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WO1997038024A1 - Catalyseur de polymerisation d'olefines, procede de polymerisation d'olefines, compositions de polymeres d'olefines et articles thermoformes - Google Patents

Catalyseur de polymerisation d'olefines, procede de polymerisation d'olefines, compositions de polymeres d'olefines et articles thermoformes Download PDF

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Publication number
WO1997038024A1
WO1997038024A1 PCT/JP1997/001217 JP9701217W WO9738024A1 WO 1997038024 A1 WO1997038024 A1 WO 1997038024A1 JP 9701217 W JP9701217 W JP 9701217W WO 9738024 A1 WO9738024 A1 WO 9738024A1
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Prior art keywords
bis
compound
group
olefin polymer
transition metal
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PCT/JP1997/001217
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English (en)
Japanese (ja)
Inventor
Kenji Sugimura
Kiyotaka Yorozu
Yasuhiko Suzuki
Tetsuo Hayashi
Shin-Ya Matsunaga
Original Assignee
Mitsui Chemicals, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP08669896A external-priority patent/JP3749756B2/ja
Priority claimed from JP8669996A external-priority patent/JPH09278824A/ja
Priority claimed from JP08865896A external-priority patent/JP3650463B2/ja
Priority claimed from JP08865996A external-priority patent/JP3650464B2/ja
Application filed by Mitsui Chemicals, Inc. filed Critical Mitsui Chemicals, Inc.
Priority to US09/155,876 priority Critical patent/US6136743A/en
Priority to KR1019980708036A priority patent/KR100311595B1/ko
Priority to CN97194688A priority patent/CN1105730C/zh
Priority to DE69731081T priority patent/DE69731081T2/de
Priority to EP97915685A priority patent/EP0893455B1/fr
Publication of WO1997038024A1 publication Critical patent/WO1997038024A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/70—Iron group metals, platinum group metals or compounds thereof
    • C08F4/7095—Cobalt, nickel or compounds thereof
    • C08F4/7098—Nickel or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/04—Broad molecular weight distribution, i.e. Mw/Mn > 6
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61904—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with another component of C08F4/60
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to an orphan polymerization catalyst, an orphan polymerization method using the catalyst, and an orphan polymer composition and a thermoformed article. More specifically, the present invention has a high polymerization activity and a wide molecular weight distribution.
  • a novel catalyst for the polymerization of olefins to obtain olefin copolymers, a method for polymerization of olefins using this catalyst, and an olefin having excellent mechanical properties and excellent moldability The present invention relates to a polymer composition and a thermoformed product obtained by thermoforming the composition. Background art
  • a titanium-based catalyst comprising a solid titanium catalyst component containing a donor and an organic aluminum compound, and a vanadium-based catalyst comprising a vanadium compound and an organic aluminum compound.
  • a Ziegler-type catalyst comprising a meta-opencane compound such as zirconocene and an organoaluminoxy compound (aluminoxane) is known. JP 7/01217
  • ethylene polymers and propylene polymers are used as various molding materials because of their excellent mechanical strength, heat resistance, transparency, and chemical properties of shochu. It is required that the olefin polymer has good moldability.
  • a catalyst comprising a nickel compound or a palladium compound as described above and a cocatalyst has a high polymerization activity, but the olefin polymer obtained by using the catalyst has a narrow molecular weight distribution and a low moldability. Is not always good. For this reason, there is a demand for an improved catalyst comprising a nickel compound or a palladium compound and a co-catalyst so that an olefin polymer having a wide molecular weight distribution and excellent moldability can be obtained without impairing high polymerization activity.
  • a catalyst comprising a nickel compound or a palladium compound as described above and a cocatalyst has a high polymerization activity, but the olefin polymer obtained by using the catalyst has a narrow molecular weight distribution and a low moldability. Is not always good. For this reason, there is a demand for an improved catalyst comprising a nickel compound or a palladium compound and a co-cataly
  • the above-mentioned polymer having excellent properties is desired to be used for a wide range of applications, and the desired properties are different depending on the application.
  • an olefin polymer having an excellent melt tension (melt tension) is required in order to prevent drawdown and the like.
  • Films are required to have impact resistance and heat resistance.
  • the properties of the Orrefin polymer have been improved in accordance with the intended use.
  • a propylene block copolymer having both a crystalline polypropylene component and a rubber component is known, and Japanese Patent Application Laid-Open No. 4-337308 discloses a silicone group-crosslinked type as a catalyst component.
  • a method for producing a propylene block copolymer having an excellent balance between impact resistance and rigidity using a catalyst containing a melamine compound is disclosed.
  • Crystalline polypropylene, rubber-like substances such as amorphous propylene or amorphous or low-crystalline ethylene / propylene random copolymer, polyisobutylene, and polybutadiene as impact modifiers There is also known a method of forming a poly (propylene) composition by blending the same with a polymer such as a crystalline propylene polymer and an amorphous ethylene propylene polymer.
  • EPR copolymer
  • the present inventor studied a catalyst capable of obtaining an olefin polymer having high polymerization activity, a wide molecular weight distribution, and excellent moldability.
  • a dime compound and (i) a meta-mouth compound or (ii) a magnesium compound Doo
  • Polymerization of olefins using a catalyst comprising a titanium catalyst component containing titanium, titanium and halogen as essential components and a co-catalyst such as an aluminoxane and an ionic compound, has excellent polymerization activity and a wide molecular weight distribution. It has been found that a refin polymer can be obtained.
  • the present inventors have studied an orefin polymer composition suitable as a thermoformed material, and found that the nickel compound or the palladium compound was combined with an aluminoxane and an ionic compound.
  • a crystalline olefin having a specific range of intrinsic viscosity, melting point, and density which is produced using an olefin polymerization catalyst comprising the nickel compound or palladium compound and a cocatalyst such as an aluminoxane or an ionic compound.
  • an olefin polymerization catalyst comprising the nickel compound or palladium compound and a cocatalyst such as an aluminoxane or an ionic compound.
  • (c) at least one compound selected from (c-1) an organic aluminum compound, (c-2) an alkylporonic acid derivative, and (c-3) a compound which reacts with a transition metal compound to form an ion pair.
  • M represents a transition metal atom belonging to Groups 8 to 10 of the periodic table
  • X 1 and X 2 may be the same or different from each other and represent a nitrogen atom or a phosphorus atom;
  • R 1 and R 2 may be the same or different from each other, and represent a hydrogen atom or a hydrocarbon group
  • n and n may be the same or different from each other, and are 1 or 2, and are numbers that satisfy the valences of X 1 and X 2 , respectively;
  • R 3 is a group binding to X 1 and X 2
  • R e , R 7 , R 6 R e2 , R 71 and R 72 may be the same or different and represent a hydrogen atom or a hydrocarbon group.
  • R 4 and R 5 may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, one OR 8 , one SR 8 , one N (R 1 () ) 2 or —P (R) 2 (however, R 8 ⁇ scale 11 alkyl group, cycloalkyl group, indicates Ariru group, Ararukiru group or an organic silyl group, R ie s or R 11 together may form a ring. And R 4 and R 5 may be linked to each other to form a ring;
  • the transition metal compound represented by the general formula (I) is preferably a compound represented by the following general formula ( ⁇ ).
  • the catalyst for polymerization of the present invention has a high polymerization activity and a high molecular weight. ⁇
  • the method for polymerizing an olefin according to the present invention is characterized in that the olefin is polymerized or copolymerized in the presence of the catalyst as described above.c
  • the olefin polymer composition according to the present invention Is an orefin polymer composition (orefin polymer) obtained by the above method. Such an olefin polymer composition has a wide molecular weight distribution and excellent moldability.
  • the intrinsic viscosity [V] measured in 135 decals is in the range of 0.5 to 20 dl / g,
  • Tg glass transition temperature measured by a differential scanning calorimeter (DSC) is ⁇ 40 ° C. or less
  • An amorphous olefin polymer 9 to 1 parts by weight;
  • Such an olefin polymer composition is excellent in moldability, and a thermoformed article obtained by heating and molding this olefin polymer composition has rigidity such as tensile modulus and shochu impact strength.
  • Another embodiment of the orefin polymer composition according to the present invention which has excellent mechanical properties, includes (A-2) a transition metal compound (b) represented by the general formula (I). s
  • Tm melting point measured by a differential scanning calorimeter
  • a crystalline olefin polymer 99-1 parts by weight
  • Such an olefin polymer composition is excellent in moldability, and a thermoformed article obtained by thermoforming the olefin polymer composition is excellent in mechanical properties and heat resistance.
  • the (B) orphan polymer may be, for example,
  • (a-2) a titanium catalyst component containing magnesium, titanium and halogen as essential components
  • (c) at least one compound selected from (c-1) an organic aluminum compound, (c-2) an alkylporonic acid derivative, and (c-3) a compound which reacts with a transition metal compound to form an ion pair.
  • FIG. 1 is an explanatory view showing one example of a preparation process of a catalyst for polymerization of an olefin according to the present invention.
  • the catalyst for polymerization of olefin according to the present invention the method for polymerizing the olefin using the catalyst, the composition of the olefin polymer, and the thermoformed article obtained by thermoforming the composition will be specifically described.
  • the term “polymerization” may be used to mean not only homopolymerization but also copolymerization.
  • the term “polymer” refers to not only homopolymer but also copolymer. It is sometimes used to include polymers.
  • (a-2) a titanium catalyst component containing magnesium, titanium and halogen as essential components
  • (c) at least one selected from the group consisting of (C-1) an organoaluminum oxy compound, (c-2) an alkylporonic acid derivative and (c-3) a compound which reacts with a transition metal compound to form an ion pair.
  • C-1 an organoaluminum oxy compound
  • c-2 an alkylporonic acid derivative
  • c-3 a compound which reacts with a transition metal compound to form an ion pair.
  • the (a-1) transition metal compound of Group 4 of the periodic table used in the present invention is a transition metal compound containing a ligand having a cyclopentagenenyl skeleton represented by the following general formula (H-1). .
  • M 1 represents a transition metal atom selected from Group 4 of the periodic table, specifically, zirconium, titanium or hafnium, and preferably zirconium.
  • X is a valence of the transition metal atom M 1, indicating the number of ligands L of coordinating to the transition metal atom M 1.
  • L represents a ligand coordinated to a transition metal atom; at least one L is a ligand having a cyclopentene genenyl skeleton; L other than a ligand having a cyclopentene genenyl skeleton is a carbon atom A hydrocarbon group having 1 to 20 carbon atoms; a halogenated hydrocarbon group having 1 to 20 carbon atoms; an oxygen-containing group; an i-containing group; a gayne-containing group; a halogen atom or a hydrogen atom.
  • Examples of the ligand having a cyclopentenyl skeleton include a cyclopentenyl group, a methylcyclopentenyl group, a dimethyl cyclopentenyl group, a trimethylcyclopentagenenyl group, a tetramethylcyclopentenyl group, Bentamethylcyclopentene Phenyl, phenylcyclopentenyl, methylethylcyclopentenyl, propylcyclopentenyl, methylpropylcyclopentagenenyl, butylcyclopentagenenyl, methylbutylcyclopentenyl, £, hexylcyclopenta
  • Examples thereof include an alkyl-substituted cyclopentenyl group such as a genenyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. These groups may be substituted with a (halogenated) hydrocarbon group having 1 to
  • the compound represented by the general formula (H -1) contains 2% or more of ligands having a cyclopentagenenyl skeleton, two of the ligands having a cyclopentenyl skeleton have the same structure. Or a (substituted) alkylene group or a (substituted) silylene group.
  • a transition metal compound in which two ligands having a cyclopentene genenyl skeleton are bonded via a divalent bonding group is represented by a general formula (1-3) described later. Transition metal compounds.
  • ligand L other than the ligand having a cyclopentene genenyl skeleton include the following.
  • hydrocarbon group having 1 to 20 carbon atoms examples include an alkyl group, a cycloalkyl group, an alkenyl group, an arylalkyl group and an aryl group, and more specifically, methyl, Alkyl groups such as ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl and aicosyl; cyclopentyl, cyclohexyl, norbornyl and ada Cycloalkyl groups such as mantyl; alkenyl groups such as vinyl, propenyl, and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, and phenylpropyl; phenyl, triyl, dimethylxyl, trimethylphenyl, Examples include aryl groups such as ethylphenyl, propylphenyl, biphenyl, naphthyl
  • halogenated hydrocarbon group having 1 to 20 carbon atoms examples include groups in which the hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen.
  • oxygen-containing group examples include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; an aryl group such as phenoxy, methyloxy, dimethylphenoxy, and naphthoxy; and phenylmethoxy. And arylalkoxy groups such as phenylethoxy.
  • Examples of the thio-containing group include a substituent in which the oxygen of the oxygen-containing group is substituted with thio, and methylsulfonate, trifluoromethansulfonate, phenylsulfonate, benzylsulfonate, P-toluenesulfonate, Sulfonate groups such as trimethylbenzenesulfonate, triisobutylbenzenesulfonate, P-chlorobenzenesulfonate, and pentafluorobenzenesulfonate;
  • Examples include sulfinate groups such as methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, and penfluorobenzenesulfinate.
  • gayne-containing groups include monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl; trimethylsilyl, triethylsilyl, triprovilsilyl, tricyclohexylsilyl, and triphenylsilyl.
  • Trisilyl ethers such as dimethylphenylsilyl, methyldiphenylsilyl, trilinolesilyl, and trinaphthylsilyl; silyl ethers of hydrocarbon substituted silyls such as trimethylsilyl ether; G-substituted alkyl groups such as methylnylmethyl; and G-substituted aryl groups such as trimethylphenyl.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Such a transition metal compound for example, when the valence of the transition metal is 4, is more specifically represented by the following general formula (H-2).
  • M 1 represents a transition metal atom selected from Group 4 of the periodic rule as described above, and is preferably a zirconium atom.
  • R 31 represents a group (ligand) having a cyclopentagenenyl skeleton
  • R 32 , R 33, and R 34 may be the same or different
  • a compound in which at least one of R 32 , R 33 and R 34 is a group (ligand) having a cyclopentadienyl skeleton for example R 31 and Fine R 3 2 is Shikuropen evening a group (ligand) which is of compound having a Jeniru skeleton is used properly preferred.
  • R 3 1 and R 3 2 is a group (ligand) having a Shikuropen evening Jeniru skeleton
  • groups R 3 3 and R 3 4 is having Shikuropen evening Jeniru skeleton, alkyl group, cycloalkyl group, alkenyl It is preferably a group, an arylalkyl group, an aryl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a sulfonate group, a halogen atom or a hydrogen atom.
  • transition metal compound represented by the general formula (H-1) and in which M 1 is zirconium are shown.
  • transition metal compound represented by the general formula (E-1) a compound in which zirconium is replaced with titanium or hafnium in the zirconium compound as described above can also be mentioned.
  • transition metal compound in which a ligand having two cyclopentagenenyl skeletons are bonded via a divalent bonding group examples include, for example, a compound represented by the following formula (1-3).
  • M 1 represents a transition metal atom of Group 4 of the periodic table, specifically, zirconium, titanium or hafnium, and preferably zirconium.
  • R 3S , R 3e , R 37 and R 38 may be the same or different from each other, and may have 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, Shows oxygen-containing group, y-containing group, gayne-containing group, nitrogen-containing group, phosphorus-containing group, halogen atom or hydrogen atom ⁇ ⁇
  • R 35 , R 3 e , R 37, and R i8 some of the groups adjacent to each other may be connected to form a ring together with the carbon atoms to which those groups are bonded.
  • R 3S , R 36 , R 37 and R 38 are each shown at two places, for example, each of R 35 and R 35 may be the same group or different groups.
  • Those denoted by the same reference symbols among the groups represented by R indicate a preferred combination when forming a ring by inheriting them.
  • hydrocarbon group having 1 to 20 carbon atoms examples include the same alkyl group, cycloalkyl group, alkenyl group, arylalkyl group and aryl group as those described above for L.
  • a ring formed by connecting a part of adjacent groups together with a carbon atom to which those groups are bonded is a benzene ring or naphthylene
  • a condensed ring group such as a ring, an acenaphthene ring and an indene ring, and a group in which a hydrogen atom on the condensed ring group is substituted with an alkyl group such as methyl, ethyl, propyl and butyl.
  • halogenated hydrocarbon group having 1 to 20 carbon atoms examples include groups in which the hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen.
  • Examples of the oxygen-containing group include a hydroxy group and the same alkoxy group, aryloxy group, aryloxy group and the like as in L.
  • Examples of the zeo-containing group include substituents in which the oxygen of the oxygen-containing group is y-substituted.
  • Examples thereof include dihydrocarbon-substituted silyl, trihydrocarbon-substituted silyl, silyl ether of hydrocarbon-substituted silyl, gayne-substituted alkyl group, and gayne-substituted aryl group.
  • nitrogen-containing group examples include amino groups; methylamino, dimethylamino, getylamino, alkylamino groups such as dipropylamino, dibutylamino, and dicyclohexylamino; and phenylamino and diphenylamino.
  • alkylamino groups such as dipropylamino, dibutylamino, and dicyclohexylamino
  • phenylamino and diphenylamino examples thereof include arylamino groups such as mino, ditriamino, dinaphthylamino, and methylphenylamino, and alkylarylamino groups.
  • Examples of the phosphorus-containing group include phosphino groups such as dimethylphosphino and diphenylphosphino.
  • halogen atom examples include the same as those described above.
  • a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom is preferable, and a hydrocarbon group having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl, or R 3 is particularly preferable.
  • R 3 6, R 3 7 and among the groups represented by R 3 8 is properly also benzene ring part of which is formed by connecting adjacent radicals of one another, hydrogen atoms on the benzene ring is methyl, It is preferably a group substituted with an alkyl group such as ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl and the like.
  • X 3 and X 4 may be the same or different from each other, and may be a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, an oxygen-containing group, , A gayne-containing group, a hydrogen atom or a halogen atom.
  • hydrocarbon group having 1 to 20 carbon atoms examples include the same Examples include a kill group, a cycloalkyl group, an alkenyl group, an arylalkyl group, and an aryl group.
  • halogenated hydrocarbon group having 1 to 20 carbon atoms examples include groups in which the hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen.
  • Examples of the oxygen-containing group include a hydroxy group and the same alkoxy group, aryloxy group, aryloxy group and the like as in L.
  • Examples of the dithio-containing group include a substituent in which the oxygen of the oxygen-containing group is substituted with dithio, a sulfonate group and a sulfinate group similar to those of L.
  • Examples of the silicon-containing group include the same gay-substituted alkyl group and gay-substituted aryl group as those described above for L.
  • halogen atom examples include the same groups and atoms as those described above for L.
  • a halogen atom a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group is preferable.
  • Y 1 is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent gayne-containing group, a divalent germanium Containing group, divalent tin containing group, one 0—, one CO—, — S—, one SO—, —S02 one, one Ge—, one Sn—, —NR 39 —.
  • P (R 39 ) One, one P (0) (R 39 )-, one BR 33 -or one A 1 R 38- [However, R 39 may be the same or different, and has 1 to 2 carbon atoms.
  • the divalent hydrocarbon group having 1 to 20 carbon atoms include methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, and 1,3-triene.
  • Alkylene groups such as dimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene; diphenylmethylene, diphthylene And arylalkylene groups such as enyl- and 2-ethylene.
  • divalent halogenated hydrocarbon group having 1 to 20 carbon atoms include groups obtained by halogenating the above divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene. No.
  • divalent gayne-containing groups include silylene, methylsilylene, dimethylsilylene, getylsilylene, di (n-propyl) silylene, and di (i-propyl) silylene.
  • divalent germanium-containing group examples include groups in which the above-mentioned divalent gayne-containing group is substituted with germanium for germanium.
  • divalent tin-containing group examples include groups in which the above-mentioned divalent gayne-containing group is substituted with tin.
  • R 39 is a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom as in L. Is an atom.
  • substituted silylene groups such as dimethylsilylene, diphenylsilylene and methylphenylsilylene are particularly preferred.
  • the transition metal compound represented by the formula (ox-3) includes a transition metal compound represented by the following general formula (1-4) or (H-5).
  • M 1 represents a transition metal atom of Group 4 of the periodic table, specifically, titanium, zirconium or hafnium, preferably zirconium.
  • R 41 may be the same or different, and represents a hydrocarbon group having 1 to 6 carbon atoms.
  • Alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl; vinyl, pro- And alkenyl groups such as dinyl.
  • a methyl group and an ethyl group are preferred.
  • R 4 2, R 4 4, R 4 5 and R 4 6, which may be the same or different from each other, a hydrogen atom, a halogen atom or R 4 1 and similar hydrocarbon group having 1 to 6 carbon atoms Show.
  • R 43 may be the same as or different from each other, and have 6 or more hydrogen atoms or carbon atoms! 6 represents an aryl group, specifically,
  • Examples include phenyl, ⁇ -naphthyl, / S-naphthyl, anthryl, phenanthryl, pyrenyl, acenaphthyl, phenalenyl, acetyltrienyl, tetrahydrodronaphthyl, indanil, biphenylyl and the like. Of these, phenyl, naphthyl, anthryl, and phenanthryl are preferred.
  • aryl groups include halogen atoms such as fluorine, chlorine, bromine and iodine;
  • Alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, iconosyl, norbornyl, and adamantyl; alkenyl groups such as vinyl, probenyl and cyclohexenyl; benzyl, Arylalkyl groups such as phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, hy- or; 8-naphthyl, methylnaphthyl, anthryl-phenanine Hydrocarbon groups having 1 to 20 carbon atoms, such as aryl groups such as tolyl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl
  • X 3 and X 4 may be the same or different from each other is the same as X 3 and X 4 in the one general formula (-3).
  • a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms is preferable.
  • Y] is similar to Upsilon 1 in the general formula (H-3).
  • a divalent gayene-containing group a divalent germanium-containing group is preferable, and a divalent gayne-containing group is more preferable.
  • Alkylsilylene, alkylarylsilylene, or ⁇ -alkylsilylene is preferable. It is particularly preferred that it is lilylsilylene.
  • transition metal compound represented by the general formula (H-4) are shown below.
  • a racemate of the transition metal compound represented by the one-branch formula (H-4) is generally used as a catalyst component, but an R-type or S-type may also be used.
  • transition metal compounds represented by the general formula (H-4) are described in Journal of Organometallic Chem. 288 (1985), pp. 63-67, European Patent Application Publication No. 0,320,762, and It can be manufactured according to the examples.
  • M 1 represents a transition metal atom of Group 4 of the periodic table, specifically, titanium, zirconium or hafnium, preferably zirconium. 701217
  • R S1 and R 52 may be the same or different from each other, and represent a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, Iou-containing group, Gay-containing group, a nitrogen-containing group, Li down-containing group, a halogen atom or a hydrogen atom, and specific examples thereof include the same atoms or groups and the R 35 to R 38.
  • R 51 is preferably a hydrocarbon group having 1 to 20 carbon atoms, and particularly preferably a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl.
  • R 52 is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, particularly a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl. It is preferred that
  • R 53 and R 54 may be the same or different from each other, and represent an alkyl group or a cycloalkyl group having 1 to 20 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n -Alkyl groups such as -butyl, isobutyl, sec-butyl, tert-butyl, n_pentyl, neopentyl, n-hexyl, cyclohexyl, octyl, nonyl, dodecyl, and iconosyl; cyclic alkyls such as norbornyl and adamantyl And the like.
  • R 53 is preferably a 2 ⁇ or 3 ⁇ alkyl group.
  • X 3 and X 4 may be the same or different from each other is the same as X 3 and X 4 in the one general formula (E-3).
  • Y 1 is the same as Y 1 in the general formula (1-3) in.
  • Specific examples of the transition metal compound represented by the above general formula (E-5) are shown below.
  • those having a branched alkyl group such as i-propyl, sec-butyl and tert-butyl at the 4-position are particularly preferred.
  • a racemic body of the transition metal compound represented by the general formula (H-5) is generally used as a catalyst component, but an R-type or S-type may also be used.
  • the transition metal compound represented by the general formula (1-5) as described above is It can be synthesized from a den derivative by a known method, for example, a method described in JP-A-4-268307.
  • (a-1) a compound represented by the following general formula (M-1) can also be used as the transition metal compound of Group 4 of the periodic table.
  • M 1 represents a transition metal atom of Group 4 of the periodic table.
  • L 2 is a derivative of a delocalized 7 ⁇ -binding group, which imparts a constrained geometry to the gold M 1 active site,
  • X 5 may be the same or different from each other, and may be a hydrogen atom, a halogen atom or a hydrocarbon group containing up to 20 carbon atoms, a gayne atom or a germanium atom, a silyl group or Is a germyl group
  • M 1 represents a transition metal atom of Group 4 of the periodic table, specifically, zirconium, titanium, or hafnium, and preferably zirconium.
  • C p represents a substituted cyclopentenyl group having a substituent Z and a derivative thereof bonded to M 1 ;
  • Z 1 is an oxygen atom, a zeolite atom, a boron atom, or 14 of the periodic table Doo 2
  • a ligand containing a group element for example
  • Y 2 represents a ligand containing a nitrogen atom, a phosphorus atom, an oxygen atom or an iodine atom, for example, one N (R 52 ) one, -0—, —S—, one ⁇
  • R 55 is a hydrogen atom or a group selected from alkyl, aryl, silyl, alkyl halide, aryl halide groups having up to 20 non-hydrogen atoms, and combinations thereof.
  • R 52 is the number of carbon atoms
  • a fused ring system of up to 0 non-hydrogen atoms may be formed.
  • transition metal compound represented by the general formula (DI-2) is shown below.
  • silane zirconium dichloride Li de (Benjirua Mi de) dimethyl - (Te Toramechiru - eta 5 - Shikurobe down evening Jeniru ) silane titanium dichloride Li de, (Fueniruhosufi de) dimethyl (Te Toramechiru - such Shikuropen evening Jeniru) Sila Njiru Koniu ⁇ dibenzyl -? 7 5.
  • titanium catalyst component containing magnesium, titanium and halogen as essential components
  • titanium catalyst component contains magnesium, titanium and halogen as essential components, and Contains an electron donor as needed.
  • Such a (a-2) titanium catalyst component can be prepared by contacting a magnesium compound and a titanium compound as described below and, if necessary, an electron donor.
  • titanium compound used for preparing the titanium catalyst component include a tetravalent titanium compound represented by the following formula.
  • R represents a hydrocarbon group
  • X represents a halogen atom
  • n is 0 ⁇ n ⁇ 4
  • TiC TiBr 4 Ti l ⁇ te tiger halogenated titanium emissions such as: Ti (OCH 3) Cl 3 , Ti (OC 2 H 5) Cl 3, T i (0 -nC 4 H s) C 1 3,
  • Monohalogenated trialkoxy such as Ti (O CH 3 ) 3 Cl, Ti (OC 2 H 5 ) 3 CK T i (0 -n- C * H 9 ) 3 CKT i (0 C 2 H 5 ) 3 Br Titanium ;
  • Tetraalkoxy titanium such as Ti (0-iso-C 4 H 9 ) 4 and Ti (0-2-ethylhexyl) 4 can be exemplified.
  • halogen-containing titanium compounds are preferred, and tetrahalogenated titanium is more preferred, and titanium tetrachloride is particularly preferred.
  • These titanium compounds may be used alone or in a combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.
  • Examples of the magnesium compound used for preparing the titanium catalyst component (a-2) include a magnesium compound having a reducing property and a magnesium compound having no reducing property.
  • the magnesium compound having a reducing property is, for example, magnesium having a magnesium carbon bond or a magnesium-hydrogen bond.
  • Nesium compounds include dimethylmagnesium, ethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamagnesium, dihexylmagnesium, didecylmagnesium, and ethylmagnesium chloride.
  • These magnesium compounds may be liquid or solid, or may be derived by reacting metal magnesium with a corresponding compound. Further, it can be derived from metallic magnesium using the above-mentioned method during the preparation of the catalyst.
  • non-reducing magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride, ethoxymagnesium chloride, and the like.
  • Alkoxy magnesium halides such as isopropoxy magnesium chloride, magnesium butoxy chloride, and octoxy magnesium chloride; aryloxy magnesium halides, such as phenoxy magnesium chloride and methyl oxymagnesium chloride; ethoxy magnesium, iso magnesium Alkoxymagnesium such as propoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium; Examples thereof include aryloxymagnesium such as simium magnesium and dimethyl phenoxymagnesium; and magnesium carboxylate such as magnesium laurate and magnesium stearate.
  • the non-reducing magnesium compound may be a compound derived from the above-described reducing magnesium compound or a compound derived during the preparation of the catalyst component.
  • a magnesium compound having a reducing property may be replaced with a halogen, a halogen-containing organic silicon compound, a halogen-containing aluminum compound,
  • the compound may be contacted with a compound having an active carbon-oxygen bond, such as a halogen compound, alcohol, ester, ketone, or aldehyde, or a polysiloxane compound.
  • the magnesium compound is a complex compound, a complex compound or a mixture of another metal compound with the above magnesium compound and another metal. There may be. Further, two or more of the above compounds may be used in combination.
  • magnesium compound used for the preparation of the titanium catalyst component (a-2) many magnesium compounds can be used in addition to those described above, but in the finally obtained titanium catalyst component (a-2), It is preferable to take the form of a halogen-containing magnesium compound. Therefore, when a halogen-free magnesium compound is used, it is preferable to carry out a contact reaction with the halogen-containing compound during the preparation.
  • a magnesium compound having no reducing property is preferable, a halogen-containing magnesium compound is more preferable, and magnesium chloride, alkoxymagnesium chloride and aryloxymagnesium chloride are particularly preferable.
  • the titanium catalyst component (a-2) it is preferable to use an electron donor, and examples of the electron donor include alcohols, phenols, ketones, aldehydes, and carboxylic acids. , Acid halides, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, ammonia, amines, nitriles, isocyanates, nitrogen-containing cyclic Compounds and oxygen-containing cyclic compounds are exemplified. More specifically,
  • Halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethyl alcohol, trichloroethanol, and tricyclohexanol, such as phenol and phenol.
  • Has a low alkyl group such as resole, xylenol, ethyl phenol, butyl phenol, nonyl phenol, cumino phenol, naphthol, etc.
  • ketones 3 carbon atoms such as acetone, methylethyl ketone, methyl ethyl butyl ketone, acetophenone, benzophenone, benzoquinone, etc. ⁇ 15 ketones:
  • Aldehydes having 2 to 15 carbon atoms such as acetate aldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde:
  • Methyl formate methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroperate, methyl ethyl dichloroacetate, methacrylate Methyl acrylate, ethyl crotonate, cyclohexyl carboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, Benzyl benzoate, Methyl toluate, Ethyl toluate, Amyl toluate, Ethyl benzoate, Methyl anilate, Ethyl anilate, Ethyl ethoxy benzoate, 7-but
  • Acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride and anisic acid chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, Ethers having 2 to 20 carbon atoms, such as amide ether, tetrahydrofuran, anisol, diphenyl ether; acetic acid ⁇ , ⁇ -dimethylamide, benzoic acid ⁇ , ⁇ -jetylamide, toluy Acid amides such as ⁇ / ⁇ -dimethyl amide;
  • Nitrites such as acetonitrile, benzonitrile, and trinitrile
  • Acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride;
  • Pyrroles such as pyrrole, methylpyrroyl, and dimethylbirol Picolin; pyrrolidine; indole; pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, Pyridines such as trimethylpyridine, phenylpyridine, benzylpyridin, and pyridin chloride; nitrogen-containing cyclic compounds such as piperidine, quinoline and isoquinoline;
  • Tetrahydrofuran 1.4-Cineol, 1,8-Cineol, Pinolfuran, Methylfuran, Dimethylfuran, Diphenylfuran, Benzofuran, Coumaran, Phthalan, Teto Examples include cyclic oxygenated compounds such as lahydropyran, pyran, and ditedropyran.
  • organic acid ester a polycarboxylic acid ester having a skeleton represented by the following general formula can be mentioned as a particularly preferred example.
  • R 81 represents a substituted or unsubstituted hydrocarbon group, 5 ⁇
  • R 85 and R ie may be the same or different from each other, and represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group; R 83 and R 84 may be the same or different from each other; It represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. R 83 and R 84 may be linked to each other to form a cyclic structure.
  • the substituent includes a hetero atom such as N, 0, or S.
  • C-0- (:, C 00R, C 00H, 0H, S 0 3 H, - C - N- C one has a group such as NH 2.
  • polycarboxylic acid ester examples include getyl conodate, dibutyl succinate, getyl methyl succinate, diisobutyl a-methyl glulate, getyl methylmalonate, getyl methylmalonate, a Getyl isopropylmalonate, getyl butylmalonate, getyl phenylmalonate, diethyl ethylmalonate, getyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butylmaleate, butylmaleine Aliphatic polycarboxylic acid esters such as getyl acid, diisopropyl methyl glutarate, pill, diallyl ethyl succinate, di-2-ethylhexyl fumarate, getyl itaconate, and dioctyl citrate;
  • Alicyclic polycarboxylates such as 1,2-cyclohexanecarboxylate getyl, 1,2-cyclohexane power diisobutyl rubrate, getyl tetrahydrophthalate, and getyl nadic acid;
  • Heterocyclic polycarboxylates such as 3,4-furandicarbonic acid and the like.
  • polyvalent carboxylic acid esters include dimethyl adipate, diisobutyl adipate, diisopropyl isopropyl sebacate, di-n-butyl sebacate, di-n-otatyl sebacate, and di-2-sebacate.
  • esters of long-chain dicarboxylic acids such as tylhexyl.
  • an organic gay compound represented by the following general formula (1V-1), a polyether compound represented by the following general formula (W-2), or the like can be used as the electron donor. .
  • n 1, 2 or 3; when n is 1, R p represents a di- or tertiary hydrocarbon group; when n is 2 or 3, R p is less
  • R p represents a secondary or tertiary hydrocarbon group, the other represents a hydrocarbon group, and a plurality of R p may be the same or different, and R is a group having 1 to 4 carbon atoms. When it is a hydrocarbon group and 4-1 is 2 or 3, R Q may be the same or different from each other.
  • the secondary or tertiary hydrocarbon group those having a cyclopentyl group, a cyclopentenyl group, a cyclopentenyl group, or a substituent And hydrocarbon groups in which the carbon adjacent to the group or Si is secondary or 3 '.
  • dimethoxysilanes particularly, dimethoxysilanes represented by the following general formula (W-3) are preferable.
  • R r and R s may be the same or different from each other, and may be a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentenyl group, a substituted cyclobenzyl group, Or a hydrocarbon group in which the carbon adjacent to S i is dicarbon or tertiary carbon.
  • organosilicon compound represented by the general formula (W-3) include dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane, and di (3- Methylcyclopentyl) dimethoxysilane, di-t-amyldimethoxysilane and the like.
  • polyether compound examples include a compound represented by the following general formula (IV_2). & 3
  • R "R 25 formula, n is an integer of 2 ⁇ n ⁇ l 0, R 1 ⁇ R 26 carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, Li down, boron and Kei R 1 to R 26 , preferably R 1 to R 2n, may represent a substituent other than a benzene ring. And the main chain may contain atoms other than carbon atoms.
  • 1,3-diethers are preferably used, and in particular, 2,2-diisobutyl-1,3-dimethoxyprono.
  • water anionic, cationic, and nonionic surfactants can also be used.
  • These electron donors are used alone or in combination of two or more.
  • a carrier-supported titanium catalyst component may be prepared using a particulate carrier (e) as described below. Can also be. ⁇
  • the titanium catalyst component (a-2) can be produced by bringing a titanium compound and a magnesium compound as described above into contact with an electron donor as required, and can be produced by any method including a known method. Can be manufactured. The above-mentioned components may be brought into contact in the presence of another reaction reagent such as, for example, silicon, phosphorus, and aluminum.
  • titanium catalyst components (a-2) The specific production method of these titanium catalyst components (a-2) will be briefly described below with several examples.
  • an example in which an electron donor is used will be described.
  • this electron donor may not necessarily be used.
  • a method comprising contacting and reacting a solution comprising a magnesium compound, an electron donor, and a hydrocarbon solvent with an organometallic compound to precipitate a solid, or contacting and reacting with a titanium compound while depositing the solid.
  • a method comprising contacting and reacting a complex comprising a magnesium compound and an electron donor with an organometallic compound, and then contacting and reacting a titanium compound.
  • An inorganic or organic carrier carrying a magnesium compound is obtained from a mixture of a magnesium compound, an electron donor, and possibly a solution containing a hydrocarbon solvent and an inorganic or organic carrier. How to make contact.
  • a method comprising contacting and reacting a complex comprising an alkoxy group-containing magnesium compound and an electron donor with a titanium compound.
  • each component may be pretreated with an electron donor and a reaction auxiliary such as z or an organic metal compound or a halogen-containing gayne compound. In this method, it is preferable to use the electron donor at least once.
  • a method of treating a solid obtained by pulverizing a magnesium compound, preferably an electron donor, and a titanium compound with any of halogen, a halogen compound and an aromatic hydrocarbon may include a step of pulverizing only the magnesium compound, or a complex compound comprising a magnesium compound and an electron donor, or a magnesium compound and a titanium compound. Further, after pulverization, pre-treatment with a reaction aid may be performed, followed by treatment with halogen or the like. Examples of the reaction assistant include an organometallic compound and a halogen-containing silicon compound.
  • a method of pulverizing a magnesium compound and then contacting and reacting with a titanium compound is preferable to use an electron donor or a reaction aid at the time of pulverization and at the time of the reaction or contact.
  • a magnesium compound such as a magnesium salt of an organic acid, an alkoxymagnesium or an aryloxymagnesium
  • a liquid magnesium compound having no reducing ability is reacted with an organometallic compound to precipitate a solid magnesium-metal (aluminum) complex, which is then reacted with an electron donor and a titanium compound. How to let.
  • the amount of each of the above components used in preparing the titanium catalyst component (a-2) varies depending on the preparation method and cannot be specified unconditionally.
  • the amount of the electron donor is 0.01 to 20 mol per mol of the magnesium compound, Preferably, it is used in an amount of 0.1 to 10 mol, and the titanium compound is used in an amount of 0.01 to 1000 mol, preferably 0.1 to 200 mol.
  • the titanium catalyst component (a-2) thus obtained contains magnesium, titanium, and halogen as essential components, and contains an electron donor as needed.
  • halogen / titanium is about 2 to 200, preferably about 4 to 100
  • the electron donor Z titanium is about 0.01 1100, preferably about 0.2-10
  • the magnesium notitane is desirably about 1-100, preferably about 2-50.
  • this titanium catalyst component (a-2) When this titanium catalyst component (a-2) is in a solid state, it contains magnesium halide having a small crystal size as compared with commercially available magnesium halide, and its specific surface area is usually about 10 m 2 / g. The above is preferably about 30 to 1000 Hi 2 , more preferably about 50 to 800 m 2 / g. You.
  • the titanium catalyst component (a-2) does not substantially change its composition by hexane washing because the above components are combined to form a catalyst component.
  • the titanium catalyst component (a-2) used in the present invention when combined with an organoaluminum, has an ethylene polymerization activity of 200 g—Volima-Zmillimol—Tix time xatm, preferably 50 Og— It is desirable to show a value of not less than xatm.
  • the (b) transition metal compound belonging to Groups 8 to 10 of the periodic table used in the present invention is a transition metal compound represented by the following general formula (I).
  • M is the periodic table 8-1 0 transition metal atoms, preferably rather nickel, palladium or platinum.
  • X 1 and X 2 may be the same or different from each other and represent a nitrogen atom or a phosphorus atom.
  • R 1 and R 2 may be the same or different from each other, and represent a hydrogen atom or a hydrocarbon group.
  • the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, a propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group.
  • Straight or branched alkyl group having 1 to 20 carbon atoms such as phenyl group, naphthyl group and other aryl group having 6 to 20 carbon atoms 7/01217
  • aryl groups include substituted aryl groups in which 1 to 5 substituents such as the alkyl group having 1 to 20 carbon atoms have been substituted.
  • m and n may be the same or different from each other and are 1 or 2, and are numbers satisfying the valences of X 1 and X 2 respectively.
  • R 3 is a group binding to X 1 and X 2
  • R 6 , R 7 , R e R e2 , R 71 and R 72 may be the same or different and represent a hydrogen atom or the same hydrocarbon group as R 1 and R 2 .
  • R 1 , R 2 , R e (or R 61 , R 62 ) and R 7 (or R 71 , R 72 ) are two or more of these, preferably adjacent groups are linked to each other,
  • the ring may form a ring with the carbon atom to which the group is attached.
  • R and R 5 may be the same or different and represent a hydrogen atom, a halogen atom or a hydrocarbon group.
  • Halogen atoms include fluorine, chlorine, bromine and iodine.
  • hydrocarbon group examples include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon atom number such as a benzyl group as in R 1 and R 2. And 7 to 20 aralkyl groups. These aryl and aralkyl groups have the carbon atom 38024
  • One or more substituents such as an alkyl group having 1 to 20 may be substituted.
  • R 4 and R 5 groups represented by one OR e , one SR 9 , —N (R 10 ) 2 or —P (RH) 2 are also indicated.
  • R 8 to Shaku 11 have the same carbon number as the above R 1 and R 2 , such as an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a cyclohexyl group.
  • an organic silyl group such as a triethylsilyl group.
  • the aryl group and the aralkyl group may be substituted with one or more substituents such as the alkyl group having 1 to 20 carbon atoms. Then, R 1Q or R 11 may be connected to each other to form a ring.
  • the above 4 and R 5 may be linked to each other to form a ring.
  • a compound represented by the following general formula ( ⁇ ) is preferable. .
  • transition metal compound represented by the one-branch formula ( ⁇ ) include the following compounds.
  • iPr represents an isopropyl group.
  • examples of the transition metal compound represented by the general formula ( ⁇ ) include a compound in which palladium or nickel in the above compound is replaced by platinum.
  • examples of the transition metal compound represented by the general formula (I) include the following compounds other than the above. Note that, in the following equation, i Pr is irib. Represents a pill group.
  • examples of the transition metal compound represented by the general formula (I) include compounds in which palladium or nickel in the above compound is replaced by platinum.
  • the above transition metal compounds are used alone or in combination of two or more.
  • the (c-1) organoaluminoxy compound used in the present invention may be a conventionally known aluminoxane, or may be a benzene-insoluble compound as exemplified in JP-A-2-77867.
  • the organic aluminum compound of the present invention may be used.
  • the conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent.
  • the aluminoxane may contain a small amount of an organic metal component.
  • the organic aluminum compound After removing the organic aluminum compound by distillation, the organic aluminum compound may be redissolved in a solvent or struck with a poor solvent for aluminoxane.
  • organic aluminum compound used when preparing the aluminum oxane are exemplified as the organic aluminum compound belonging to (d-1) in the description of (d) the organic metal compound described later.
  • Organic aluminum compounds and the like can be mentioned. Of these, trialkyl aluminum and trialkyl aluminum are preferred, and trimethyl aluminum is particularly preferred.
  • Such organic aluminum compounds are used alone or in combination of two or more.
  • Solvents used in the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, zidylene, cumene, and simene; pentane, hexane, heptane, octane, decane, dodecane, and hexadeca. Alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene, and gas oil or the above aromatics Specific examples include hydrocarbon solvents such as hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbon halides, and chlorinated and brominated compounds. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.
  • the A1 component soluble in 60 benzenes is usually 10 or less, preferably 5% or less, particularly preferably 2% or less in terms of A1 atoms.
  • the (a-1) organoaluminoxy compound as described above is used alone or in combination of two or more.
  • Examples of the alkylboronic acid derivative (c-2) used in the present invention include a compound represented by the following general formula (V).
  • R 12 represents a hydrocarbon group having 1 to 10 carbon atoms.
  • R 13 may be the same or different, and represents a hydrogen atom, a halogen atom, a siroquine group, a lower alkyl-substituted siloxy group, or a hydrocarbon group having 1 to 10 carbon atoms.
  • alkylboronic acid derivative represented by the general formula (V) is the same as the alkylboronic acid represented by the following general formula (VI).
  • R 12 represents the same group as R 12 in the general formula (V).
  • An organic aluminum compound is reacted with an organic aluminum compound in an inert solvent under an inert gas atmosphere in an inert solvent. It can be produced by reacting at a temperature of C to room temperature for 1 minute to 24 hours.
  • alkylboronic acid represented by the general formula (VI) include methylboronic acid, ethylboronic acid, isopropylboronic acid n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, and n-butylboronic acid.
  • methylboronic acid n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylpoic acid are preferred.
  • alkylboronic acids are used alone or in combination of two or more.
  • organoaluminum compound to be reacted with the alkylboronic acid examples include an organoaluminum compound represented by the following general formula (VII-1), (II-2) or (VC-3).
  • Y represents a hydrogen atom or a halogen atom
  • R 14 represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms
  • ⁇ is 0 or 3
  • R 13 is It represents the same group as R 13 in formula (V).
  • organic aluminum compound represented by the general formula (YE-I), (VII-2) or (VC-3) will be described later in the description of (d) the organic metal compound (d-
  • the organic aluminum compounds exemplified as the organic aluminum compounds belonging to 1) are exemplified. Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferred.
  • organic aluminum The compound is used alone or in combination of two or more.
  • the above (c-2) alkylboronic acid derivatives are used alone or in combination of two or more.
  • (c-3) A compound that forms an ion pair by reacting with a transition metal compound A compound that forms an ion pair by reacting with a transition metal compound used in the present invention (c-3) (hereinafter referred to as “ionized ionic compound”). Is a compound that forms an ion pair by reacting with the transition metal compound (a-1) and the transition metal compound (b) or the transition metal compound (b).
  • No. 0 195 Japanese Patent Application Laid-Open No. Hei 11-502 036, Japanese Patent Application Laid-Open No. 3-179905, Japanese Patent Application Laid-Open No. 3-179906, Japanese Patent Application Lewis acids, ionic compounds, borane compounds, and the like described in US Pat. No. 2,073,073, Japanese Patent Laid-Open No. 3-207,704, US Pat. No. 5,321,106 and the like. Carborane compounds and the like 0
  • the Lewis acid is represented by BR 3 (R is a phenyl group which may have a substituent such as fluorine, a methyl group, a trifluoromethyl group, or fluorine).
  • Compounds include, for example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) ) Boron, tris (pentafluorene phenyl) boron, tris (P-tril) boron, tris (0-tril) boron, tris (3,5-dimethylphenyl) boron, etc. No.
  • R 1 9 the R 1 5, H +, carbonium Niu arm cation, Okisoniu Mukachion, ammonium Niu arm cation, phosphonyl ⁇ beam cation, consequent opening heptyl preparative Rie two Rukachion, etc. Fuweroseniumu cation having a transition metal No.
  • R 18 to R 13 may be the same or different and are an organic group, preferably an aryl group or a substituted aryl group.
  • carbonate cation examples include tri-substituted carbon cations such as triphenylcarbonate, tri (methylphenyl) carbonate, and tri (dimethylphenyl) carbonate.
  • ammonium cation examples include trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation.
  • Trialkylammonium cations such as ⁇ , ⁇ -ethylenilani cation, ⁇ , ⁇ -2,4,6-dimethyl ⁇ , ⁇ -dialkyl, such as methyl aniline cation
  • dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation.
  • phosphonium cation examples include triphenylphosphonium cations, triphosphine cations such as tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.
  • R 15 a carbonium cation, an ammonium cation, and the like are preferable, and a triphenylcarbonate cation and an ⁇ -methyl phenylanimium cation are particularly preferable.
  • a boron compound represented by the following formula (II) is preferable.
  • ⁇ ⁇ represents an ethyl group.
  • examples of the ionic compound include trialkyl-substituted ammonium salts, ⁇ , ⁇ -dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.
  • trialkyl-substituted ammonium salts include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri ( ⁇ -butyl) ammoniumtetratra (phenyl) boron, Trimethylammonium tetra ( ⁇ -tolyl) Boron, trimethylammonium tetra (0-tolyl) hydrogen, tri ( ⁇ -butyl) ammonium tetra (pentafluorophenyl) Boron, tripropylammonium tetra (0, ⁇ -dimethyl so
  • N, N-dialkylanilinium salts include, for example, ⁇ , ⁇ ⁇ ⁇ ⁇ -dimethylaniliniumtetra (phenyl) boron, ⁇ , ⁇ -jetylanilininimutene tra (phenyl) boron, IV-2, 4. 6-Bentamethylanilinetetra (phenyl) boron.
  • dialkylammonium salt examples include di (1-butoxypyr) ammonium tetra (borane fluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.
  • borane compound examples include decaborane (14): bis [tri ( ⁇ -butyl) ammonium] nonaborate, bis [tri ( ⁇ -butyl) ammonium] decaborate, bis [tri ( ⁇ ) -Butyl) ammonium] Indecaborate, bis [tri ( ⁇ -butyl) ammonium] dodecaborate, bis [tri ( ⁇ -butyl) ammonium] decachlorodecaborate, bis [tri ( salt of anion such as dodecachlorododecaborate; tri (II-butyl) ammonium bis (dodeforce hydride dodecaborate) cobaltate ( ⁇ ), bis [tri (n- (Butyl) ammonium) bis (dode force high dry dodecaborate) Metal borane such as nickelate (M) Such as salt, and the like.
  • decaborane (14) bis [tri ( ⁇ -butyl) ammonium] nonaborate, bis [tri ( ⁇ -
  • carborane compounds include, for example, 4-carpanonaborane (14), 1,3-dicarpanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydrido-1-phenyl-1,3 -Dicarpanona borane, dodeca hydride-1-methyl-1,3-dicarpanona borane, panda power high hydride-1,3-dimethyl-1,3,3-dicar panona borane, 7, 8-dical pound borne (13), 2,7-dicarboundecaborane
  • Decahydride-7,8-dicarbaundecaborate) aurate (1), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7.8-dicarpoune) Deborate) ferrate (I), tri (n-butyl) ammonium bis (nonahydride)-7,8-dimethyl-7,8-dicarpound decaborate chromate (11 ), Tri (n-butyl) ammonium bis (tripromo hydride, 7,8-dicarbadecaneborate) Cobaltate (), Tris [tri (n-butyl) ammonium] Bis (Pindecahydrate-7-Caloundecarborate) Chromate ( ⁇ ), Bis (tri (n-butyl) ammonium) Bis (Pindecahydride-7-Calpoundecarborate) Manganate (W ) , Screw ⁇ Li (n-butyl) ammonium) Bis (ndecahydride -7-potassium carbonate) co
  • the catalyst for polymerization of olefin comprises a transition metal compound (a-1) belonging to Group 4 of the periodic table or a titanium catalyst component (a-2) containing magnesium, titanium and halogen as essential components; Group 8-10 transition metal compounds (b), at least one selected from (c-1) organic aluminum oxy compounds, (c-2) alkylporonic acid derivatives and (c-3) ionized ionic compounds
  • the compound is formed from the species compound (c), and if necessary, an organometallic compound (d) and a particulate carrier (e) as described below.
  • Etc. can also be used.
  • organometallic compound used as required in the present invention include organometallic compounds of Groups 1 and 2 and Groups 12 and 13 of the periodic table as described below.
  • R * and Rb may be the same or different from each other, and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and X represents a halogen atom.
  • M is 0 and m ⁇ 3
  • II is On and 3
  • p is 0 ⁇ p ⁇ 3.
  • M 2 represents Li, Na, or K
  • R * represents a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms.
  • R * and Rb may be the same or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M 3 is Mg, Zn Or C d.
  • organoaluminum compound belonging to (d-1) examples include the following compounds.
  • R ′ and Rb may be the same or different from each other, and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and m is preferably 1.5. ⁇ m ⁇ 3.
  • R ′ represents a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms
  • X represents a halogen atom
  • m is preferably 0 ⁇ m ⁇ 3.
  • R * represents a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and m is preferably 2 ⁇ m ⁇ 3.
  • organoaluminum compound belonging to the above (d-1) trimethylaluminum, triethylaluminum, lipaluminum pillaluminum, trin-butylaluminum, tripentylaluminum Tri-n-alkyl aluminum such as trihexyl aluminum, trioctyl aluminum and tridecyl aluminum;
  • Tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum:
  • Tri-fin aluminum such as tri-phenyl aluminum and tri-tri aluminum
  • Dialkyl aluminum hydride such as getyl aluminum hydride and diisobutyl aluminum hydride
  • Trialkenyl aluminum such as trisoprenyl aluminum
  • Alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, and isobutyl aluminum isopropoxide:
  • Dialkylaluminum alkoxides such as dimethylaluminum methoxide, dimethylaluminum ethoxide, getylaluminum ethoxide, dibutylaluminum butoxide; SI
  • Alkyl aluminum sesquialkoxides such as ethyl mini sesquioxide and butyl aluminum sesquioxide;
  • Dialkylaluminum aryloxides such as getyl aluminum phenoxide
  • Dialkylaluminum chlorides such as dimethylaluminum chloride, getylaluminum chloride, dibutylaluminium chloride, diisobutylaluminum chloride, and getylaluminum bromide;
  • Alkyl aluminum sesquichlorides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide;
  • Partially halogenated alkyl aluminum such as alkyl aluminum dihalide such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide; etc .; getyl aluminum hydride, dibutyl aluminum hydride Dialkyl aluminum hydrides such as
  • alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
  • Partially alkoxylated and halogenated alkyl aluminum such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, and ethyl aluminum ethyne bromide Is mentioned.
  • compounds similar to the above (d-1) can be used, and examples thereof include an organic aluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom.
  • examples thereof include:
  • Compounds belonging to the above (d-2) include:
  • Li A1 (C 2 H S ) 4 Li A1 (C7H 1 S ) 4 and the like.
  • Examples of the compound belonging to (d-3) include dimethylmagnesium, dimethylmagnesium, dibutylmagnesium, butylethylmagnesium and the like.
  • organometallic compound (d) methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride Lid, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride, etc. can also be used.
  • a compound which forms the above-mentioned organic aluminum compound in the polymerization system for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium can be used. .
  • organometallic compound (d) used in the present invention a branched-chain 01217
  • a metal compound having an alkyl group is preferable, and a metal compound having an isobutyl group is particularly preferable, and a triisobutyl metal compound is particularly preferable.
  • Aluminum is preferred as the metal, and triisobutyl aluminum is most preferred.
  • Such an organometallic compound (d) acts as an alkylating agent, and R 4 and / or R 5 bonded to the transition metal () in the transition metal compound (b) represented by the general formula (I).
  • Such an alkyl-substituted transition metal compound (b) reacts with the component (c), particularly (c-3), an ionized ionic compound to form an ionic complex having high catalytic activity.
  • the organometallic compound also acts as a scavenger, removing water and other impurities from the system to keep the reaction system clean, so that the catalyst can exhibit a high activity stably.
  • the effect is obtained.
  • This effect is also exhibited when R 4 and Z or R 6 bound to the transition metal (M) in the transition metal compound (b) are alkyl groups.
  • the organometallic compound (d) was used in combination with the transition metal compound (b) in which R 4 and R or R 5 bonded to the transition metal (M) in the one-branch type (I) are alkyl groups. In such a case, the above effect as a scavenger can be obtained.
  • the (d) organometallic compound as described above is used alone or in combination of two or more.
  • the fine particle carrier used as required in the present invention is an inorganic or organic compound, and has a particle size of 10 to 300 m, preferably 20 to 200 m. Solids in the form of particles or fine particles are used. Among them, a porous oxide is preferable as the inorganic compound.
  • Si 0 2 , A 12 0 3 , Mg 0> Z r 0, Ti 0 2 , B 2 0 3 , Ca 0, Z n 0, B a 0, Th 0 2 etc., or mixtures containing them were example, if Si0 2 -Ntg 0, S i02- a 1 2 03, S iO 2 -T iO 2, Si_ ⁇ 2 - V 2 0 5 , S i0 2 -Cr 2 03, Si0 2 -Ti0 like 2 -Mg O can illustrate to Rukoto a. At least selected from the group consisting of S i 0 2 and A1 2 0 3 in these as a main component one of the components preferred.
  • the above inorganic oxide small amount of Na 2 C 0 3, K 2 C 0 3, CaC0 3, g C 03, Na 2 S 0 *, A1 2 (S 04) 3, B a S 0 *, KN0 3 , g (N 0 3) 2 A1 (N0 3) 3 Na 2 0, K 2 0, carbonates such as Li 2 0, sulfate, nitrate, it may safely be contained oxide component.
  • the particulate carrier preferably used in the present invention has a specific surface area of 50 to 100 m 2 / g, preferably 1 to 100 m 2 / g. Desirably, the pore volume is in the range of 0 to 700 mVg and the pore volume is in the range of 0.3 to 2.5 cmVg. Microparticles Fushimi carriers 0 1 0 0-1 0 0 optionally e C, is favored properly 1 5 0-7 0 0. Used by firing in C.
  • examples of the particulate carrier (e) that can be used in the present invention include a granular or particulate solid of an organic compound having a particle size in a range of 10 to 300 m.
  • organic compounds include carbon sources such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene.
  • examples thereof include (co) polymers formed mainly of -olefins having 2 to 14 carbon atoms or (co) polymers formed mainly of vinylcyclohexane and styrene.
  • the catalyst for polymerization of an olefin according to the present invention comprises a transition metal compound of Group 4 of the periodic table (a-1) or a titanium catalyst component (a-2) containing magnesium, titanium and halogen as essential components.
  • a-1 a transition metal compound of Group 4 of the periodic table
  • a-2 a titanium catalyst component
  • c-1 an organoaluminoxy compound
  • C-2 an alkylboronic acid derivative
  • c-3 an ionized ionic compound. It consists of at least one compound (c) selected, an organometallic compound (d) and, if necessary, a particulate carrier (e).
  • a catalyst component comprising the component (a-1) and the component (b) supported on a carrier (e), ⁇ 2
  • the component (d) may be used as necessary.
  • a solid catalyst component wherein the component (a-1) and the component (c) are supported on the carrier (e), and a solid catalyst wherein the component (b) and the component (c) are supported on the carrier (e)
  • the catalyst component may have a prepolymerized orefin.
  • the contact product and the component (a-1) (or the component (a-2) ) And may be added to the polymerization vessel.
  • R 21 represents a hydrocarbon group
  • the Zeta theta derived from (c-1) organoaluminum ⁇ Muo alkoxy compound, (c-2) alkyl Poron acid derivative and (c-3) at least selected from the ionizing ionic compound one compound (c) Indicates an anion.
  • R 21 is a hydrocarbon group (for example, an alkyl group) of R 4 or R 5 in the general formula (I), or The alkyl group to be introduced.
  • An anion for example, an anion forming the (c-3) ionized ionic compound, and specific examples thereof include a boron compound anion represented by the following formula (XII).
  • the boron compound anion represented by the formula (xa) is an anion derived from the boron compound represented by the formula ( ⁇ ).
  • ⁇ other than the above include, for example, anion derived from tetrax (pentafluorophenyl) borate, tetra (phenyl) boron, or the like.
  • the ionic coordination compound represented by the general formula (si) includes an ether compound (ether molecule) formed from the component (c) upon contact of the transition metal compound (b) with the component (c). May coordinate to the transition metal indicated by M.
  • Such an ionizable coordination compound is represented by the following general formula (XI-2).
  • R 21 and Zeta theta are the same as those in the general formula (XI-1),
  • R 22 represents an ether compound (ether molecule) formed from the component (c) upon contact of the transition metal compound (b) with the component (c).
  • the ether compound represented by R 22 in the general formula (XI-2) (as concrete of E one ether molecule), dimethyl ether, Jechi ether, jib port pills ether, dibutyl ether like et be.
  • ionic coordination compound represented by the general formula (II-2) examples include an ionic coordination compound represented by the following formula.
  • i Pr represents an isopropyl group and Et represents an ethyl group.
  • the component (b) is brought into contact with the component (c) and, if necessary, the component (d) in advance to obtain the compound represented by the general formula (XI
  • the component (b) and the component (c), and if necessary, the component (d) are mixed in the reaction medium.
  • the reaction is carried out at a temperature of 0 to 120, preferably 180 to 120 "C, for 5 minutes to 100 hours, preferably 30 minutes to 5 hours.
  • reaction medium examples include hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene, and xylene.
  • Inert hydrocarbons; halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane, and chlorobenzene can be used.
  • an alkyl (meth) acrylate may be allowed to coexist. In this case, it is preferable to use (c-3) an ionized ionizable compound as the component (c).
  • Examples of the (meth) acrylic acid alkyl ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and n-acrylic acid. Butyl, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, ⁇ -propyl methacrylate, Examples include isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate.
  • the compound is represented by the following general formula (III-3) It is presumed that an ionic coordination compound is formed.
  • R 23 represents a residue of a hydrocarbon group
  • R 24 and R 25 represent some of the residues of the alkyl (meth) acrylate.
  • R 23 is a hydrocarbon group of R 4 or R 5 in the general formula (I) (for example, a residue of an alkyl group), or (d) an organometallic compound Is a residue of an alkyl group introduced by
  • R 23 Specific examples of the group represented by R 23 include:
  • R 2 * and R 25 represent (meth) acrylic acid alkyl ester upon contact of the transition metal compound (b) with (meth) acrylic acid alkyl ester. Is part of the residue formed from
  • R 24 Specific examples of the group represented by R 24 include:
  • ionic coordination compound represented by the general formula (XI-3) include an ionic coordination compound represented by the following formula.
  • i Pr represents an isopropyl group.
  • the component (b) and the component (c) are contacted in advance with the component (d) if necessary in the presence of the alkyl (meth) acrylate ester, and the component (b) is represented by the above-mentioned single branch type (X [-3).
  • the component (b) and the component (c) and, if necessary, the component (d) are added in the presence of an alkyl (meth) acrylate to the same reaction medium as described above. In—120- + 40. C, preferably — 80-0.
  • the reaction is carried out at a temperature of C for 5 minutes to 100 hours, preferably for 30 to 5 hours.
  • the amount of the (meth) acrylic acid alkyl ester used is usually from 0.3 to 3, preferably from 0.8 to 3, in terms of the molar ratio of the (meth) acrylic acid alkyl ester to the component (b). 1.1 is preferred.
  • an olefin polymer is obtained by polymerizing or copolymerizing the olefin in the presence of the above-described catalyst for olefin polymerization.
  • the polymerization can be carried out by any of a liquid phase polymerization method such as solution polymerization and suspension polymerization or a gas phase polymerization method.
  • the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; Alicyclic hydrocarbons such as benzene, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, and mixtures thereof. And the olefin itself can be used as a solvent.
  • aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene
  • Alicyclic hydrocarbons such as benzene, cyclohexane, and
  • component (a-1) when performing polymerization of Orefi emissions, component (a-1), the reaction volume one liter per usually 1 0 one 8 ⁇ 1 (J - 3 moles, Preferably, it is used in an amount of from 10 to 7 to 10 to 4 mol, and the component (a-2) is usually 10 to 8 in terms of titanium atom per liter of reaction volume.
  • Component (b) is usually used in an amount of from 10 to 1 mol per liter of reaction volume, preferably from 10 to 3 mol, preferably from 10 to 7 to 10 to 4 mol. (It is used in an amount such that J- 3 mol, preferably 1 ⁇ - 7 to ⁇ 0 mol. Also, component (b) is combined with component (b). ⁇
  • the molar ratio to the component (a-1) (or component (a-2)) is usually 0.02 to It is used in an amount such that it is 100, preferably 0.05 to 50.
  • the component (c-1) and the component (c-2) are composed of the aluminum atom in the component (c-1) and the aluminum atom in the component (C-2), and the component (a-1) (or the component (a -2)) and the molar ratio C (cl) ZM or (c-2) / M) of all transition metal atoms (M) in component (b) are usually 10 to 500 More preferably, it is used in such an amount that it becomes 20 to 2000.
  • Component (c-3) is the molar ratio of component (c-3) to component (a-1) (or component (a-2)) and all transition metal atoms (M) in component (b) [ (C-3) ZM] is used for i such that it is usually 1 to 10, preferably 1 to 5.
  • the component (d) used as necessary is a mole of the component (d) and the component (a-1) (or the component (a-2)) and all the transition metal atoms (M) in the component (b). It is used in such an amount that the ratio [(d) /) is usually 0.01 to 500, preferably 0.05 to 2000.
  • Polymerization temperature Orefu fin using such Orefi emissions polymerization catalyst is usually - in 5 0-2 0 0, preferably in the range of 0 ⁇ 1 7 0 e C.
  • the polymerization pressure is usually normal pressure ⁇ 1 0 0kg / cm 2, preferably under conditions of normal pressure ⁇ 5 0 kg / cm 2, the polymerization reaction is a batch, semi-continuous, in any of the methods of continuous Can also be done. Further, the polymerization can be performed in two or more stages under different reaction conditions.
  • the molecular weight of the resulting olefin polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. 7/01217
  • Examples of the orphan which can be polymerized by such an orphan polymerization catalyst include those having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, and the like. 1-pentene, 3-methyl-1-butene, trihexene, 4-methyl-topentene, 3-methyl-topentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1- Hexadecene, 1-octadecene, trieicosen;
  • Cyclic olefins having 3 to 20 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1, 2,3,4,4a, 5,8,8a-octahydronaphthalene.
  • styrene, vinylcyclohexane, and gen may be used.
  • the catalyst for polymerization of the olefin according to the present invention has a high polymerization activity, and an olefin polymer having a wide molecular weight distribution can be obtained.
  • the olefin polymer composition (the olefin polymer) obtained using the olefin polymerization catalyst according to the present invention has a wide molecular weight distribution and excellent moldability. Further, when two or more kinds of orifices are polymerized using the orefin polymerization catalyst according to the present invention, an orifice polymer having a narrow composition distribution can be produced.
  • the orefin polymer composition according to the present invention includes an amorphous orefin polymer (A-1) which is produced using a specific catalyst and has specific physical properties. (B) and crystalline materials that have been produced using specific catalysts and have specific physical properties. There is a polymer formed from an orefin polymer (A-2) and another conventionally known orefin polymer (B).
  • the amorphous olefin polymer (A-1) is produced using a specific catalyst, and has the following properties.
  • the glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) is 140 ° C or lower, preferably ⁇ 45′C or lower, more preferably 150 ° C or lower. It is.
  • the density is 0.88 g / cm 3 or less, preferably 0.875 g / cm 3 or less, and more preferably 0.870 g / cm 3 or less.
  • the amorphous orefin polymer (A-1) may be a homopolymer of orefine or a copolymer of orefin as long as it is an amorphous orefin polymer satisfying the above characteristics. Or a copolymer of an orifice and another monomer.
  • the copolymer may be a random copolymer or a block copolymer.
  • the ⁇ -olefin having 2 to 20 carbon atoms and the carbon atom having 3 carbon atoms are the same as those exemplified as the orifices that can be polymerized by the above-mentioned polymerization catalyst.
  • the orifices that can be polymerized by the above-mentioned polymerization catalyst.
  • a vinyl compound, a silane-based unsaturated compound, a polyene compound, or the like can be used as a monomer to be copolymerized with the olefin.
  • aromatic vinyls such as styrene, substituted styrenes, arylbenzenes, substituted arylbenzenes, vinylnaphthylenes, substituted vinylnaphthalenes, arylnaphthalenes, and substituted arylnaphthalenes
  • aromatic vinyls such as styrene, substituted styrenes, arylbenzenes, substituted arylbenzenes, vinylnaphthylenes, substituted vinylnaphthalenes, arylnaphthalenes, and substituted arylnaphthalenes
  • Alicyclic vinyl compounds such as vinylcyclopentane, substituted vinylcyclopentanes, vinylcyclohexane, substituted vinylcyclohexanes, vinylcyclohexane, substituted vinylcycloheptane, and rilnorbornane;
  • Aryl trimethylsilane, aryl triethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1-hexene, 8-trimethylsilyl-1-octene, 10-to Silane-based unsaturated compounds such as methylsilyl-1-decene can be used.
  • ethylene homopolymers and copolymers of ethylene and other orefins are particularly preferred.
  • the amorphous olefin polymer (A-1) is produced using a catalyst containing the transition metal compound (b) represented by the general formula (I), and the catalyst comprises a transition metal compound (A).
  • a catalyst containing the transition metal compound (b) represented by the general formula (I) for example, a compound which reacts with (c-1) an organoaluminoxy compound, (c-2) an alkylboronic acid derivative and (c-3) a transition metal compound to form an ion pair It is preferably formed using at least one selected compound.
  • the transition metal compound (b) is added in an amount of about 10 to 1 millimol per 1 liter of the reaction volume. , preferably 1 0 - used in an amount such that the 4 to 1 Mi Rimoru.
  • the organoaluminum oxy compound (c-1) or the alkylporonic acid derivative (c-2) is used as a cocatalyst component, the component (c-1) or the component (c-2) is not included in these components.
  • the molar ratio [(cl) or (c-2) / (b)] between the aluminum atom and the transition metal compound (b) is usually 10 to 100, preferably 20 to 500
  • the molar ratio of the ionized ionic compound (c-3) to the transition metal compound (b) [(c- 3) / (b)] is preferably 1 to 10 and preferably 1 to 5.
  • the organometallic compound (d) has a molar ratio (: (d) / (b)) of the organometallic compound (d) to the transition metal compound component (b) of 0.01 to 100, preferably It is used as needed in such an amount as to be 0.05 to 50.
  • the order of contact is not particularly limited. In this case, the contact can be performed at a temperature of about 100 to 150. C, preferably about -80 to 120. In the case of the contact, an inert hydrocarbon solvent may be used. it can.
  • the catalyst may be used after prepolymerizing orffins.
  • the amorphous olefin polymer (A-1) polymerizes the above-mentioned olefins in the presence of the above-mentioned catalyst so as to groove the above-mentioned properties (Ai-CA! -S) ( Or copolymerization).
  • the polymerization can be performed by any of a gas phase polymerization method, a slurry polymerization method, and a liquid phase polymerization method such as a solution polymerization method.
  • Inert hydrocarbons can be used as polymerization medium, for example propane, butane, isopropane 1
  • Aliphatic hydrocarbons such as butane, pentane, hexane, octane, decane, dodecane, hexadecane, octadecane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, and cyclooctane; benzene, Aromatic hydrocarbons such as toluene and xylene; petroleum fractions such as gasoline, kerosene, and gas oil can be used. Of these, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferred. In liquid phase polymerization, the olefin itself, which is liquid at the time of polymerization, may be used as a solvent.
  • the polymerization temperature is usually 150 to 100 when slurry polymerization is carried out.
  • C preferably in the range of 0 to 90 ° C., and usually in the range of 0 to 200 ° C., preferably 10 to 180 ° C. when performing solution polymerization. In practice, it is usually in the range of 0 to 120, preferably in the range of 20 to 100.
  • the polymerization pressure is from normal pressure to 100 kg / cm 2 , preferably from normal pressure to 50 kg / cm 2 .
  • the polymerization may be performed in any of a batch system, a semi-continuous system, and a continuous system, and may be performed in two or more stages under different reaction conditions.
  • the molecular weight of the obtained amorphous olefin polymer (A-1) can be adjusted using hydrogen or the like.
  • Crystalline Orefi down polymer (A-2) is produced using a specific catalyst, and has the following characteristics ( ⁇ 2 -1) ⁇ ( ⁇ 2 -3).
  • the melting point (Tm) measured by differential scanning calorimetry (DSC) is 60
  • the crystalline olefin polymer (A-2) may be a homopolymer of olefin or a copolymer of olefin as long as the crystalline olefin polymer satisfies the above characteristics. Alternatively, it may be a copolymer of the olefin and another monomer. The copolymer may be a random copolymer or a block copolymer.
  • olefin examples include the same polyolefins having 2 to 20 carbon atoms and those having 3 carbon atoms, similar to those exemplified as the olefins which can be polymerized by the above-mentioned catalyst for polymerization of olefin.
  • olefins having 2 to 20 carbon atoms and those having 3 carbon atoms, similar to those exemplified as the olefins which can be polymerized by the above-mentioned catalyst for polymerization of olefin.
  • a vinyl compound, a silane-based unsaturated compound, a boron compound, or the like similar to those used in producing the amorphous olefin polymer (A-1) may be used.
  • olefin polymers an ethylene homopolymer and a copolymer of ethylene and ⁇ -olefin are particularly preferable.
  • the crystalline olefin polymer ( ⁇ -2) is produced using a catalyst containing the transition metal compound (b) represented by the general formula (I).
  • the medium reacts with the transition metal compound (b) as a cocatalyst component, for example, by reacting with the aforementioned (c-1) organoaluminoxy compound, (c-2) alkylboronic acid derivative and (c-3) transition metal compound. It is preferably formed using at least one compound selected from compounds forming an ion pair.
  • the transition metal compound (b) In the production of crystalline Orefui down polymer (A -2) using a catalyst component as described above, the transition metal compound (b), the reaction volume one liter per about 1 0 - 5 to 1 Mi It is desirable to use the compound in an amount such that the amount is 10 mols, preferably 10 4 to 1 mol.
  • an organic aluminum methoxy compound (c-1) or an alkylboronic acid derivative (C-2) is used as a cocatalyst component
  • (C-1) or (c-2) is used in these components.
  • the molar ratio [(cl) or (c-2) (b)] of the aluminum atom of (a) to the transition metal compound (b) is usually 10 to 100, preferably 20 to 500.
  • the ionized ionic compound (c-3) is used as the cocatalyst component
  • the molar ratio of the ionized ionic compound (c-3) to the transition metal compound (b) [(c -3) / (b)] is preferably 1 to 10 and more preferably 1 to 5.
  • the organometallic compound (d) has a molar ratio (: (d) / (b)) of the organometallic compound (d) to the transition metal compound component (b) of 0.01 to 100, preferably 0.05 to 100. It is used as needed in such an amount as to give 50.
  • the order of contact is not particularly limited. In this case, the temperature is about 100 to 150 ° C, preferably about 180 to 120 ° C. Can be brought into contact in advance. At the time of contact, an inert hydrocarbon solvent can be used.
  • the catalyst may be used after prepolymerizing orffins.
  • the polymerization can be performed by any of a gas phase polymerization method, a slurry polymerization method, and a liquid phase polymerization method such as a solution polymerization method.
  • a gas phase polymerization method a slurry polymerization method
  • a liquid phase polymerization method such as a solution polymerization method.
  • the same inert hydrocarbons as those used for producing the amorphous olefin polymer (A-1) can be used. Of these, aliphatic hydrocarbons, alicyclic hydrocarbons, and petroleum fractions are preferred.
  • the olefin itself which is liquid at the time of polymerization may be used as a solvent.
  • the polymerization temperature is usually in the range of ⁇ 500 to 100 when the slurry polymerization is carried out, preferably in the range of 900 eC, and is usually 200 in the case of carrying out the solution polymerization. (: Preferably in the range of 110 180, and usually in the range of 120, preferably 210 0 C when performing gas phase polymerization.
  • the polymerization pressure is to no normal pressure 1 0 0 kgZcni 2, is preferably carried out in the normal pressure ⁇ 5 0 kg / cm 2.
  • the polymerization may be performed in any of a batch system, a semi-gun system, and a continuous system, and may be performed in two or more stages under different reaction conditions.
  • the molecular weight of (A-2) can be adjusted. ioq
  • the olefin polymer (B) is different from the catalyst used in the production of the amorphous olefin polymer (A-1) and the crystalline olefin polymer (A-2) as described above.
  • the catalyst is not particularly limited except that it is produced using a catalyst.
  • a catalyst component of a meta-acetate compound such as a transition metal compound (a-1) of Group 4 of the periodic table as described above, It can be produced by a known method using a conventionally known solid titanium catalyst component such as a natural titanium catalyst component (a-2).
  • the orefin polymer (B) is any organic compound.
  • the orefin polymer (B) is any organic compound.
  • (c) at least one compound selected from (c-1) an organic aluminum compound, (c-2) an alkyl polonic acid derivative and (c-3) an ionized ionizable compound;
  • the olefin polymer (B) may be an olefin homopolymer or a copolymer of two or more types of olefins.
  • the copolymer may be a block copolymer. Or a random copolymer.
  • the orefin having the same number of carbon atoms as 2 to 20 and the number of carbon atoms of 3 to 20 similar to those exemplified as the orefin which can be polymerized by the above-mentioned catalyst for polymerization of orefin is used.
  • 20 cyclic or the like.
  • styrene or the like may be copolymerized with these orifices.
  • the olefin polymer (B) is preferably a polymer whose main constituent unit is a unit derived from an olefin having 2 to 6 carbon atoms, and particularly a unit derived from ethylene or propylene.
  • ethylene polymer or a propylene polymer having as a main structural unit it is preferably an ethylene polymer or a propylene polymer having as a main structural unit. More specifically, the units derived from ethylene or propylene may be used in an amount of 80 to 100 mol%, preferably 90 to 100 mol%, more preferably 92 to 100 mol%. An ethylene polymer or a propylene polymer contained in a proportion is preferred.
  • a propylene polymer contains 0 to 10 mol%, preferably 0 to 8 mol%, more preferably 0 to 6 mol, of units derived from ethylene as another ore, and has 4 carbon atoms. It is desirable to contain units derived from ⁇ 12 orphans in a proportion of 0 to 15 mol%, preferably 0 to 10 mol%, more preferably 0 to 5 mol.
  • the olefin polymer (B) used in the present invention is, in addition to the unit derived from the above-mentioned olefin, particularly an olefin having a branched structure or a borylene having 4 to 20 carbon atoms. May be contained in a proportion of 5 mol% or less.
  • branched olefins include 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-pentene, and 4-methyl- 1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, arylnaphtha Len, arylenobornane, styrene, dimethylstyrene, vinylnaphthalene, aryltoluene, aryl Benzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, etc.
  • borenes include 1,3-butadiene, 1,3-pentagen, 1,4-pentane, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-6,6 -Octadien, 6-Propyl-1,6-Oxengen, 6-Butyl-1,6-Oxengen, 6-Methyl-1,6-Nonadiene, 7-Methyl-1,6 -Nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl -1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1 , 6-pentadecadiene, 1,7-oc
  • the intrinsic viscosity measured in decalin at 135 is as follows. [7?] Is in the range of 0.5 to 20 dl / g, preferably 0.7 to 1 Odl / g, and the melting point (Tm) measured by the differential scanning calorimeter (DSC) is 1 0 0 hand above, preferred properly is in the range of 1 1 0 ⁇ 1 6 7 'C , density 0.85 ⁇ 1. 0 g / cm 3, is favored properly 0. 8 7 0 ⁇ 0. 9 7 5 g / It is desirable to be in the range of cm 3 .
  • the extreme polymer measured in decal is 135.
  • viscosity [] is 0. 5 ⁇ 2 0 dl / g, and preferred rather is in the range of 0. 7 ⁇ 1 O dl / g, density 0.85 ⁇ 0.98 g / cm 3, preferred ⁇ 12.
  • the melting point ( ⁇ is obtained as the temperature at the maximum peak position in an endothermic curve measured by a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the orefin polymer composition according to the present invention includes:
  • (B) 1 to 99 parts by weight of the olefin polymer, preferably 30 to 95 parts by weight, more preferably 50 to 90 parts by weight (provided that (A-1) and (B) (The total amount is 100 parts by weight).
  • (A-2) a crystalline olefin polymer in an amount of 99 to 1 part by weight, preferably 95 to 5 parts by weight, more preferably 90 to 10 parts by weight,
  • (B) 1 to 99 parts by weight of the olefin polymer, preferably 5 to 95 parts by weight, more preferably 10 to 90 parts by weight (provided that (A-2) and (B) In some embodiments, the total amount is 100 parts by weight.
  • the olefin polymer composition according to the present invention can be prepared by a method generally known as a method for preparing a resin composition.
  • a method for preparing a resin composition For example, an amorphous olefin polymer (A-1) (Or the crystalline olefin polymer (A-2)) and the olefin polymer (B) by melt-kneading.
  • (c) at least one selected from the group consisting of (C-1) an organoaluminum oxy compound, (c-2) an alkylporonic acid derivative and (c-3) a compound which reacts with a transition metal compound to form an ion pair.
  • C-1 an organoaluminum oxy compound
  • c-2 an alkylporonic acid derivative
  • c-3 a compound which reacts with a transition metal compound to form an ion pair.
  • Melt flow rate (MFR: 230 ° C. according to AST D1238-65T) of an olefin polymer composition comprising an amorphous olefin polymer (A-1) and an olefin polymer (B) (: Measured under a load of 2.16 kg) should be in the range of 0.01 to 1000 g / 10 min, preferably 0.1 to 100 g / 10 min.
  • melt index (Ml: 190 ° in accordance with ASTM D1238-65T) of an olefin polymer composition comprising a crystalline olefin polymer (A-2) and an olefin polymer (B).
  • C measured under a load of 2.16 kg
  • the olefin polymer composition comprising the amorphous olefin polymer (A-1) and the olefin polymer (B) as described above has excellent rigidity such as tensile modulus and impact resistance. Are better. More amorphous If the olefin polymer (A-1) and the olefin polymer (B) are selected and used so as to have different melt flow rates, the moldability can be further improved.
  • the above-mentioned crystalline polymer composition comprising the crystalline polymer (A-2) and the polymer (B) has a high melt tension, excellent moldability, A molded article having excellent mechanical strength and heat resistance can be obtained.
  • the amorphous polymer composition according to the present invention comprises the above-described amorphous olefin polymer (A-1) (or crystalline olefin polymer (A-2)) and In addition to the refin polymer (B), if necessary, additives and other polymers may be contained as long as the object of the present invention is not impaired. An appropriate amount of a rubber component or the like for improvement may be contained.
  • Additives include nucleating agents, antioxidants, hydrochloric acid absorbers, heat stabilizers, weather stabilizers, light stabilizers, ultraviolet absorbers, slip agents, antiblocking agents, anti-violent agents, lubricants, Antistatic agents, flame retardants, pigments, dyes, dispersants, copper damage inhibitors, neutralizing agents, foaming agents, plasticizers, foam inhibitors, crosslinking agents, flow improvers such as peroxides, gels Strength improvers, natural oils, synthetic oils, waxes and the like.
  • nucleating agents such as peroxides, gels Strength improvers, natural oils, synthetic oils, waxes and the like.
  • nucleating agent various conventionally known nucleating agents can be used without any particular limitation. Among them, the following nucleating agents are preferably used. 1217
  • R 1 represents oxygen, sulfur or a hydrocarbon group having 1 to 10 carbon atoms
  • R 2 and R 3 may be the same or different from each other, and have a hydrogen or carbon number of 1 indicates ⁇ 1 0 a hydrocarbon group, R 2 to each other, may have a ring by bonding R 3 s or R 2 and R 3,
  • M represents a 1 to trivalent metal atom
  • n represents 1 It is an integer of ⁇ 3.
  • sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate sodium-2,2'-ethylidene-bis (4, 6-di-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i-propyl-6-t-butylphenyl) phosphate, Lithium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, calcium -Bis [2,2'-thiobis (4-methyl-6-t-butylphenyl)
  • R 4 represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms
  • M represents a monovalent to trivalent metal atom
  • n represents an integer of 1 to 3.
  • Sodium-bis (4-t-butylphenyl) phosphate sodium-bis (4-methylphenyl) phosphate, sodium-bis (4-ethylphenyl) phosphate , Sodium-bis (4-i-propylphenyl) phosphate, sodium-bis (4-octylphenyl) phosphate, potassium-bis (4-t-butylphenyl) Phosphate, calcium-bis (4-t-butylphenyl) phosphate, magnesium-bis (4-t-butylphenyl) phosphate, lithium-bis (4-t-butylphenyl) phosphate, Aluminum-bis (4-t-butyl Phenyl) phosphite and a mixture of two or more thereof.
  • R s is hydrogen or indicate to a hydrocarbon group having a carbon number of 1 to 0.
  • 1.3,2,4-dibenzylidenesorbitol 1.3-benzylidene-2,4-p-methylbenzylidenesorbitol, 1,3-benzylidene-2,4-p-ethylbenzyl Liden sorbitol, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-ethylbenzylidene-, 4-benzylidene sorbitol, 1,3- ⁇ -methylbenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3,2,4-di (P-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3,2,4-di (pn-propy
  • 1,3.2,4-dibenzylidene sorbitol 1,3,2,4-di (P-methylbenzylidene) sorbitol, 1,3,2,4-di (P-ethylbenzylidene) Sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol and mixtures of two or more of these Is preferred.
  • examples of the nucleating agent include metal salts of aromatic carboxylic acids or aliphatic carboxylic acids, such as aluminum benzoate, aluminum pt-butyl benzoate, sodium adipate, and thiophene carboxylic acid.
  • metal salts of aromatic carboxylic acids or aliphatic carboxylic acids such as aluminum benzoate, aluminum pt-butyl benzoate, sodium adipate, and thiophene carboxylic acid.
  • Sodium and sodium pyrocarboxylate are exemplified.
  • an inorganic compound such as talc described later can also be used as a nucleating agent.
  • the nucleating agent may be an amorphous olefin polymer (A-1) (or a crystalline olefin polymer (A-2)) and an olefin.
  • A-1 amorphous olefin polymer
  • A-2 crystalline olefin polymer
  • olefin amorphous olefin polymer
  • 0.001 to 10 parts by weight preferably 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight in total with the copolymer (B). It is desirable that it be contained in an amount of about parts by weight.
  • Antioxidants include phenol-based antioxidants and sulfur-based oxidants. ⁇ 2C
  • An antioxidant a phosphorus-based antioxidant, and the like can be used.
  • phenolic antioxidants examples include 2,6-di-tert-butyl-p-crelaub, stearyl (3,3-dimethyl-4-hydroxybenzyl) thioglycolate, Stearinole- (4-Hydrokine-3,5-di-tert-butyl phenol) propionate, distearyl-3,5-di-tert-butyl-4-hydroxybenzyl Phosphonate, 2,4,6-tris (3'.5'-di-tert-butyl-4'-hydroxybenzylthio) -1,3,5-triazine, distearyl (4- Hydroquinine-3-methyl-5-tert-butylbenzyl) malonate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-methylenebis (2,6- Di-tert-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) P-cresol], bis [3,5
  • sulfur-based antioxidants examples include dialkylthiodipropionates such as dilauryl-, dimethyl- and distearyl- and alkyls such as butyl-, octyl-, laurinole- and stearyl-.
  • Esters of polyhydric alcohols of luthiopropionic acid for example, glycerin, trimethylolethane, trimethylolpronone, pentaerythritol, trishydroxyshetyl isocyanurate
  • Penyu Eri Suri Thorte Tralauri Liothiopropionate).
  • phosphorus antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenylphosphite, and tris (2,4- Di-tert-butylphenyl) phosphite, triphenyl phosphite, tris (butoxyshethyl) phosphite, tris (nonylphenyl) phosphite, distaryl pentyl erythritol diphosphite, tetra (g Rideshi Le) -1, 1, 3-Application Benefits scan (2-methyl -5-tert-butyl - 4-arsenide Dorokishifu et two Le) butane diphosphite phi DOO, Te tiger (C 12 -C iota 5 mixture Alkyl) -4,4'-isopropylidenediphenyl
  • Pen erythritol diphosphite bis (2,4-di-tert-butylphenyl) Pencil erythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tris [4,4'-isopropylidenebis (2-tert- Butylphenol)] phosphite, phenyl'diisodecylphosphite, di (nonylphenyl) penyl erythritol diphosphite), tris (1,3-di-stearoyl quinoline) Phosphite, 4,4'-isobutyl pyridenebis (2-tert-butylphenol) 'di (nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-9-oxa Examples include -10-phos
  • 6-hydroquin chroman derivatives such as ⁇ 7,5 various tocofurols or mixtures thereof, 2- (4-methyl-penta-3-enynole) -6-hydroxy 2,5-Dimethyl substituted cycloman, 2,5,8-Trimethyl substituted, 2,5,7,8-Tetramethyl substituted, 2,2,7-Trimethyl-5-tert -Butyl-6-hydroxycycloman, 2,2,5-trimethyl-7-tert-butyl-6-Hydroxycycloman, 2,2,5-trimethyl-6-tert-butyl-6 -Hydroxycycloman, 2,2-dimethyl-5-tert-butyl-6-hydroxycycloman, etc.
  • M x A (OH) 2 , y - 2l (A) r ⁇ A H 2 0 wenty three
  • M represents Mg, Ca or Zn
  • A represents an anion other than a hydroxyl group
  • x, y and z are each a positive number which may be the same or different, and a is 0 or a positive number is there
  • Mg 6 A1 2 (OH) isC 0 3 ⁇ 4 H 20
  • Z ⁇ ⁇ ⁇ 1 2 (0 H) isC 03 4 H 2 0,
  • M g 6 A 1 2 (0 H) i 2 C 0 a 3 H 2 can and Mochiiruko 0, for example as the hydrochloride absorber.
  • light stabilizers examples include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone-2,2'-di-hydroxy-4- Hydroxybenzophenones such as toxicbenzophenone and 2,4-dihydroxyquinbenzophenone, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy Benzotriazoles such as Droquin-5'-methylphenyl) benbuttriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriaryl; phenylzari Shire 12
  • P-tert-butylphenylsalicylate 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5 Benzoates such as -di-tert-butyl-4-hydroxybenzoate, 2.2'-thiobis (4-tert-octylphenol) Ni salt,
  • aliphatic hydrocarbons such as paraffin wax, polyethylene wax, and polypropylene wax, powerpurines, lauric acid, myristic acid, palmitic acid, and malagarin
  • Higher fatty acids such as acids, stearic acid, arachidic acid, behenic acid or metal salts thereof (eg, lithium salt, calcium salt, sodium salt, magnesium salt, calcium salt, etc.)
  • Fat-preventing alcohols such as valmicil alcohol, cetyl alcohol, and stearyl alcohol ⁇ twenty five
  • Fats such as amides, cabron amides, caprylic acid amides, cabric acid amides, paralic acid amides, myristic acid amides, palmitic acid amides, and stearic acid amides
  • Fluoride compounds such as aliphatic amides, esters of aliphatic and alcohol, fluoroalkyl carboxylic acids or metal salts thereof, and fluorinated alkylsulfonic acid gold salts.
  • the additives as described above may be contained in the olefin polymer composition in a ratio of 0.0001 to 10% by weight.
  • the orefin resin composition according to the present invention includes silica, gay alga earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite. , Calcium sulfate, calcium titanate, barium sulfate, calcium sulfite, talc, cres, my strength, asbestos, glass fibers, glass flakes, glass beads, calcium gayate, monmorillonite , Bentonite, Graphite, Aluminum powder, Molybdenum sulfide, Boron fiber, Gay carbon fiber, Polyethylene fiber, Polypropylene fiber, Polyester fiber, Polyamide fiber, Polyamide fiber, etc. Good.
  • the orefin polymer composition according to the present invention is further improved in physical property balance, durability, paintability and printability. Scratch resistance, moldability and the like. A compact can be formed.
  • the above-mentioned olefin polymer composition of the present invention can be widely used for conventionally known polyolefins.
  • the combined composition can be used, for example, by thermoforming into a sheet, unstretched or stretched film, film, or other molded articles of various shapes.
  • thermoformed body examples include known thermoforming methods such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, calendar molding, and foam molding.
  • known thermoforming methods such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, calendar molding, and foam molding.
  • the obtained molded article is exemplified.
  • the thermoformed body will be described below with several examples.
  • thermoformed product according to the present invention is, for example, an extruded product
  • its shape and product type are not particularly limited, but, for example, sheets, films (unstretched), pipes, hoses, wire coatings, and films. And the like, and particularly preferred are sheets, films, and filaments.
  • a conventionally known extruder and molding conditions can be employed, such as a single screw extruder, a kneading extruder, a ram extruder, and the like.
  • the molten polymer composition can be extruded from a T-die or the like using a gear extruder or the like to form a sheet or a film (unstretched).
  • the stretched film is formed by stretching the above-described extruded sheet or extruded film (unstretched) by a known stretching method such as a tenter method (longitudinal and transverse stretching, transverse and longitudinal stretching), a simultaneous biaxial stretching method, and a uniaxial stretching method. Can be obtained.
  • the stretching ratio when stretching a sheet or unstretched film is usually about 20 to 70 times for biaxial stretching, and usually for uniaxial stretching.
  • an inflation film can be manufactured as a film-shaped molded body.
  • the olefin polymer composition composed of the crystalline olefin polymer (A-2) and the olefin polymer (B) has a high melt tension, and may cause drawdown during inflation molding. Since it is difficult to wake up, it is suitable as a material for inflation.
  • the olefin polymer composition comprising the amorphous olefin polymer (A-1) and the olefin polymer (B) among the olefin polymer compositions according to the present invention.
  • Sheets and film moldings obtained from products are resistant to electrification, rigidity such as tensile modulus, heat resistance, impact resistance, aging resistance, transparency, transparency, gloss, rigidity, and moisture resistance It has excellent gas barrier properties and can be used widely as packaging films.
  • the sheet and the film molded product obtained from the olefin polymer composition composed of the crystalline olefin polymer (A-2) and the olefin polymer (B) have a property such as tear strength. Excellent mechanical properties, heat resistance, impact resistance, aging resistance, transparency-transparency, gloss, rigidity, moisture resistance and gas barrier properties.
  • Sheets and films obtained by thermoforming the orifice polymer composition according to the present invention are particularly excellent in moisture-proof properties, and are therefore used in press-through packs used for packaging tablets and capsules of chemicals. hrough pack).
  • the filament can be produced, for example, by extruding a molten olefin polymer composition through a spinneret.
  • the filament thus obtained may be further stretched. This post The stretching may be performed at least to such an extent that the molecules are oriented in at least one uniaxial direction, and it is usually desirable to perform the stretching at a magnification of about 5 to 10 times.
  • a fibrous material obtained from an orefin polymer composition comprising an amorphous orefin polymer (A-1) and an orefin polymer (B).
  • the laminant has excellent rigidity, heat resistance and impact resistance.
  • the filament obtained from the olefin polymer composition comprising the crystalline olefin polymer (A-2) and the olefin polymer (B) is hardly charged, and the Excellent mechanical properties.
  • the injection molded article can be produced by injection molding the olefin polymer composition into various shapes using a conventionally known injection molding apparatus and under known conditions.
  • Injection molded articles obtained from the olefin polymer composition comprising the amorphous olefin polymer (A-1) and the olefin polymer (B) among the olefin polymer compositions according to the present invention are rigid. It has excellent heat resistance, heat resistance, surface gloss, chemical resistance, and abrasion resistance.
  • an injection molded article obtained from an olefin polymer composition comprising a crystalline olefin polymer (A-2) and an olefin polymer (B) has mechanical properties such as tear strength. It excels in heat resistance, shock resistance, surface gloss, chemical resistance, and abrasion resistance.
  • the injection-molded article made of the orefin polymer composition according to the present invention can be widely used for trim materials for automobile interiors, exterior materials for automobiles, housings for home electric appliances, various containers, and the like.
  • the blow molded article is obtained by blow molding an orifice polymer composition using a conventionally known blow molding apparatus under known conditions. Can be manufactured.
  • the above-mentioned polymer composition is extruded from a die in a molten state at a resin temperature of 100 ° C. to 300 ° C. to form a tubular parison, and then the parison has a desired shape.
  • the blowing air was kept in a mold, it is possible to manufacture a hollow molded body by Rukoto be worn in the mold at a resin temperature 1 3 0 e C ⁇ 3 0 0 .
  • Stretching Professional
  • the magnification is desirably about 1.5 to 5 times in the horizontal direction.
  • the Orefi down polymer composition is injected into parison mold at a resin temperature 1 0 0 ° C ⁇ 3 0 0 e C molding the parison, then the desired shape parison After holding in the mold, air is blown, and the resin is mounted on the mold at a resin temperature of 120 to 300 ° C., whereby a hollow molded body can be manufactured.
  • the stretching (blow) magnification is desirably 1.1 to 1.8 times in the longitudinal direction and 1.3 to 2.5 times in the lateral direction.
  • blow-molded article obtained from the olefin polymer composition comprising the amorphous olefin polymer (A-1) and the olefin polymer (B) among the olefin polymer compositions according to the present invention is It has excellent rigidity, heat resistance and shochu impact resistance, as well as excellent moisture resistance.
  • blow molded articles obtained from the olefin polymer composition comprising the crystalline olefin polymer (A-2) and the olefin polymer (B) have mechanical properties such as tear strength.
  • Molding stamping moldings are examples of press moldings. For example, a base material and a skin material are simultaneously pressed to form a composite integrated molding. (Mold stamping molding) is performed according to the present invention. It can be formed from a refined polymer composition.
  • cold stamping molded body examples include automotive interior materials such as door trim, rear package trim, seat knock garnish, instrument panel and the like.
  • a press molded product obtained from an orefin polymer composition comprising an amorphous orefin polymer (A-1) and an orefin polymer (B) among the orefin polymer compositions according to the present invention has a rigidity. Excellent in heat resistance, heat resistance, aging resistance, surface gloss, chemical resistance, and abrasion resistance.
  • a press molded product obtained from an olefin polymer composition comprising a crystalline olefin polymer (A-2) and an olefin polymer (B) has good mechanical properties such as tear strength, heat resistance and impact resistance. Excellent in heat resistance, aging resistance, surface gloss, chemical resistance, abrasion resistance, etc. The invention's effect
  • the catalyst for polymerization of an olefin according to the present invention has a high polymerization activity, and an olefin polymer having a wide distribution of molecules i can be obtained.
  • the olefin polymer obtained by using the olefin polymerization catalyst according to the present invention has a wide molecular weight distribution and excellent moldability.
  • an olefin polymer composition which is excellent in rigidity such as tensile elastic modulus and mechanical properties such as shochu impact strength, and which is excellent in moldability, and rigidity and mechanical properties of this composition.
  • a thermoformed article having excellent properties or an orefin polymer composition having excellent mechanical properties and heat resistance and excellent moldability, and a thermoformed article comprising this composition and having excellent mechanical properties and heat resistance are obtained. can get.
  • the molecular weight distribution (MwZMn) of the polymer was determined by gel permeation chromatography (GPC) at 140 using 0-dichlorobenzene as a solvent.
  • the intrinsic viscosity [V] was measured in 135 decalins.
  • the glass transition temperature (Tg) and melting point (Tm) were determined by measuring with a differential scanning calorimeter at a heating rate of 1 O e CZ, respectively.
  • the density was measured using a density gradient tube.
  • YM tensile modulus
  • IZ Izod impact strength
  • Meltoindex (Ml) was measured at 190 ° C and under a load of 2.16 kg according to ASTM D256.
  • the melt tension (MT) is measured using a melt tension tester manufactured by Toyo Seiki Co., Ltd. when the strand extruded at a constant speed is measured at 190 ° C-extrusion speed of 15 thighs. It was determined by measuring the tension applied to the specimen.
  • the film impact strength was measured with a pendulum-type film impact tester (film impact tester) manufactured by Toyo Machinery Works.
  • Example 1 0.05 mmol of bis (1,2,4-trimethylcyclopentene zirconium dichloride) and 0.05 mol of the transition metal compound (1) were used.
  • Example 1 In the same manner as in Example 1 except that only bis (1.2,4-trimethylcyclopentene genyl) zirconium dichloride was used in an amount of 0.005 mol instead of the mixture with ethylene, Polymerized with propylene. As a result, Mw is 1. 9 X 1 0 5, Mw / Mn is 2. Polymer 8. 2 g was obtained 1. Comparative Example 2
  • Example i 0.005 mol of bis (1,2,4-trimethylcyclopentadenyl) zirconium dichloride and the transition metal compound (1) 0.05 Ethylene and propylene were polymerized in the same manner as in Example 1 except that only 0.05 mol of the transition metal compound (1) was used instead of the mixture with mol.
  • M w is 4. a 3 X 1 0 4, Mw / Mn of 1. 8.
  • Example 1 0.05 mmol of bis (1,2,4-trimethylcyclopentene zirconium dichloride) and 0.05 mol of the above-mentioned transition metal compound (1) were used.
  • Example 1 except that a mixture of bis (indenyl) zirconium dichloride 0.001 millimol and the transition metal compound (1) 0.005 millimol was used in place of the mixture of In the same manner as described above, ethylene and propylene were polymerized. As a result, Mw is 1. 8 X 1 0 5, MwZ Mn is Borima one 1 3. 8 g was obtained which is 4.8.
  • Example 2 bis (indenyl) zirconium zirconium dichloride 0.00.01 mmol and the transition metal compound (1) 0.005 mmol were replaced with a mixture of bis (indenyl) Ethylene and propylene were polymerized in the same manner as in Example 2 except that only 0.01 mol of zirconium dichloride was used. As a result, 7.3 g of a polymer having Mw of 3.3 ⁇ 10 5 and MwZ Mn of 2.9 was obtained.
  • Example 1 the bis (1,2,4-trimethylcyclopentene I3 ⁇
  • Example 3 instead of a mixture of 0.001 mmol of bis (1,3-dimethylcyclopentenyl) hafnium dichloride and 0.05 mol of the transition metal compound (2), Ethylene and propylene were polymerized in the same manner as in Example 3 except that only bis (1,3-dimethylcyclopentenyl) diphenyldichloride was used for 0.01 mmol.
  • Mw is 3. a 2 1 0 5, Mw Roh Mn of 2.
  • the volume Rimmer 4. 9 g of 3 was obtained.
  • Example 3 0.001 mol of bis (1,3-dimethylcyclopentagenenyl) diphenyldichloride and the transition metal compound (2) [35-
  • Ethylene and propylene were polymerized in the same manner as in Example 3 except that 0.05 mol of the transition metal compound (2) alone was used instead of the mixture with 0.05 mol of mol. did. As a result, 3.9 g of a polymer having an Mw of 7.8 ⁇ 10 4 and an Mw / Mn of 1.9 was obtained.
  • Ethylene gas was continuously supplied at a rate of 200 liters Z hours, and polymerization was carried out at 25 "C for 10 minutes under normal pressure. After the polymerization was completed, a small amount of methanol was added to carry out the polymerization. addition was stopped. the polymer solution into a large excess of main evening Nord to precipitate Borima one, was dried for 12 hours under reduced pressure at 1 3 0 ° C. As a result, Mw is at 1. 5 X 1 0 5 In this way, 3,9 g of Bolima having an Mw / Mn of 4.6 was obtained.
  • Example 4 0.005 mol of bis (1,2,4-trimethylcyclopentene gen) zirconium dichloride and 0.05 mol of the transition metal compound (1) were used. In the same manner as in Example 4 except that only bis (1,2,4-trimethylcyclopentagenenyl) zirconium dichloride was used in an amount of 0.005 mol instead of the mixture with ethylene glycol. T / JP97 / 01217
  • Example 4 0.05 mol of bis (1,2,4-trimethylcyclopentene gen) zirconium dichloride and 0.05 mol of the transition metal compound (1) were used. Ethylene and 1-octene were polymerized in the same manner as in Example 4 except that only 0.05 mol of the transition metal compound (1) was used instead of the mixture of the above. As a result, 1.8 g of a borimer having M w of 5.2 ⁇ 10 4 and M w / M n of 1 ⁇ 9 was obtained.
  • Example 5 a mixture of 0.002 mol of bis (1,3-dimethylcyclopentenyl) zirconium dichloride and 0.05 mol of the above-mentioned transition metal compound (1) was used. Instead of using only bis (1,3-dimethylcyclopentenyl) zirconium dichloride in 0.02 mmol, and triphenylcarbenyltetrax (pentafluorophenyl) vole Ethylene and propylene were polymerized in the same manner as in Example 5 except that the used amount of propylene was changed from 0.006 millimol to 0.004 millimol. As a result, 4.2 g of a polymer having M w of 2.6 ⁇ 10 5 and M wZMn of 2.2 was obtained.
  • Example 5 a mixture of 0.002 mol of bis (1,3-dimethylcyclopentagenenyl) zirconium dichloride and 0.05 mol of the above-mentioned transition metal compound (1) was added. Instead, ethylene and propylene were polymerized in the same manner as in Example 5 except that only 0.05 mol of the transition metal compound (1) was used. As a result, 3.7 g of a polymer having an Mw of 5.6 ⁇ 10 * and an MwZMn of 1.9 was obtained.
  • Example 6 the titanium catalyst component (a-1) was replaced with 0.04 g atom in terms of titanium atom and 0.02 mmol of the transition metal compound (1), and Only titanium catalyst component (a-1) is converted to titanium atom Ethylene and propylene were polymerized in the same manner as in Example 6, except that 0.004 gram atom was used in terms of conversion. As a result, 2.4 g of a polymer having Mw of 4.2 ⁇ 10 5 and MwZ Mn of 5.9 was obtained.
  • Example 6 the titanium catalyst component (a-1) was replaced with 0.04 g atom in terms of titanium atom and 0.02 mmol of the transition metal compound (1), and Ethylene and propylene were polymerized in the same manner as in Example 6, except that only 0.02 mmol of the transition metal compound (1) was used. As a result, 3.9 g of a polymer having Mw of 3.8 ⁇ 1 and Mw / Mn of 1.8 was obtained.
  • Example 7 Comparative Example 1 2
  • the above titanium catalyst component (a-1) was replaced with 0.03 g atom in terms of titanium atom and 0.02 mmol of the transition metal compound (2), and Ethylene and butene were polymerized in the same manner as in Example 7, except that only the titanium catalyst component (a-1) was used in an amount of 0.003 gram atom in terms of titanium atom.
  • 3.1 g of a polymer having an Mw of 3.7 ⁇ 10 s and an MwZMn of 6.1 was obtained.
  • Example 7 in place of the titanium catalyst component (a-1) 0.003 gram atom in terms of titanium atom and the transition metal compound 2 0.002 millimol, the transition metal Ethylene and butene were polymerized in the same manner as in Example 7 except that only Compound II was used in an amount of 0.002 mmol.
  • Mw is 2.
  • Mw / Mn is Borima one 3. 4 g was obtained which is 1.9.
  • the polymer was added to a large excess of methanol to precipitate the polymer and dried under reduced pressure at 130 for 12 hours. As a result, 47.0 g of an ethylene / propylene copolymer (A-II) shown in Table 1 was obtained.
  • the tensile modulus (YM) and the Izod impact strength (I Z) of the obtained olefin polymer composition were measured. Table 1 shows the results.
  • Example 8 was repeated in the same manner as in Example 8 except that the ethylene-propylene copolymer (A-2) obtained in Production Example 2 was used instead of the ethylene homopolymer (A-1). Thus, an olefin polymer composition was obtained. result Are shown in Table 1.
  • Example 8 was repeated in the same manner as in Example 8 except that the ethylene / hobutene copolymer (A-3) obtained in Production Example 3 was used instead of the ethylene homopolymer (A-1). Thus, an olefin polymer composition was obtained. Table 1 shows the results.
  • Example 8 to 10 the propylene homopolymer (B-III) used in Examples 8 to 10 was used without using the olefin polymer (A-1), and an antioxidant and a hydrochloric acid absorbent were used.
  • An olefin polymer composition was obtained in the same manner as in Examples 8 to 10, except that was added. Table 1 shows the results.
  • Example 8 in place of the propylene homopolymer (B-II), an ethylene homopolymer (B-II) (Mitsui An olefin polymer composition was obtained in the same manner as in Example 8, except that Petrochemical Industry Co., Ltd., trade name Hi-Zex HZ 1700J) was used. Table 1 shows the results.
  • Example 11 an antioxidant and a hydrochloric acid absorbent were added to the ethylene homopolymer (A-II) used in Example 11 without using the olefin polymer (A-1). Except for that, the procedure of Example 11 was repeated to obtain an olefin polymer composition. Table 1 shows the results. & 1
  • the polymer solution was added to a large excess of methanol to precipitate a polymer, and dried under reduced pressure at 80 ° C for 12 hours. As a result, 42.7 g of an ethylene homopolymer (A-II) shown in Table 2 was obtained.
  • Table 2 shows the melt index (Ml) and the melt tension (MT) of the obtained olefin polymer composition.
  • Example 12 was repeated except that 20 parts by weight of an ethylene homopolymer (B-II) as shown in Table 2 produced by a high-pressure radical method was used as the olefin polymer (B). In the same manner, an orefin polymer composition and an inflation film were obtained. Table 2 shows the results.
  • the ethylene-butene copolymer (B-II) as shown in Table 2 was produced using a known vanadium catalyst as the olefin polymer (B). In the same manner as in Example 12, an orefin polymer composition and an inflation film were obtained. Table 2 shows the results. Table 2

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Abstract

Cette invention concerne un catalyseur qui possède une action de polymérisation élevée et qui permet de produire des polymères d'oléfines ayant une plage étendue de poids moléculaire. Ce catalyseur comprend les éléments suivants: (a) un composé métallocène (a-1) ou un composant catalyseur à base de titane (a-2) qui comprend du magnésium, du titane et un halogène en qualité de composants essentiels; et (b) un co-catalyseur ainsi qu'un composé d'un métal de transition des groupes 8 à 10 correspondant à la formule générale (I') où M représente Pd, Ni ou Pt, tandis que X1 et X2 représentent N ou P. R1 et R2 représentent H ou un radical hydrocarbure, R4 et R5 représentent un halogène ou un radical hydrocarbure, et R6 et R7 représentent H ou un radical hydrocarbure. Cette invention concerne également une composition de polymères qui possède une excellente rigidité ainsi qu'une excellente résistance aux impacts, laquelle composition est obtenue à l'aide d'un catalyseur contenant le composé de métal de transition susmentionné (b). Cette composition comprend, d'une part, un polymère d'oléfine non cristallin qui possède une viscosité intrinsèque, une température de transition du verre et une densité données selon des plages particulières respectives et, d'autre part, un polymère d'oléfine traditionnel autre que le polymère d'oléfine susmentionné. Cette invention concerne également une autre composition de polymères d'oléfine qui possède d'excellentes propriétés mécaniques et de résistance à la chaleur, laquelle composition est obtenue à l'aide d'un catalyseur contenant le composé de métal de transition susmentionné (b). Cette composition comprend, d'une part, un polymère d'oléfine cristallin qui possède une viscosité intrinsèque, un point de fusion et une densité donnés selon des plages particulières respectives et, d'autre part, un polymère d'oléfine traditionnel autre que le polymère d'oléfine susmentionné.
PCT/JP1997/001217 1996-04-09 1997-04-09 Catalyseur de polymerisation d'olefines, procede de polymerisation d'olefines, compositions de polymeres d'olefines et articles thermoformes WO1997038024A1 (fr)

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US09/155,876 US6136743A (en) 1996-04-09 1997-04-09 Olefin polymerization catalyst, olefins polymerization methods, and olefin polymer compositions, and heat molded products
KR1019980708036A KR100311595B1 (ko) 1996-04-09 1997-04-09 올레핀중합촉매,올레핀중합방법,및올레핀중합체조성물
CN97194688A CN1105730C (zh) 1996-04-09 1997-04-09 烯烃聚合催化剂及烯烃聚合方法,以及烯烃聚合物组合物和热模塑产品
DE69731081T DE69731081T2 (de) 1996-04-09 1997-04-09 Olefin-polymerisationskatalysator, olefin-polymerisations verfahren, olefin-polymerzusammensetzungen und in der wärme geformte gegenstände
EP97915685A EP0893455B1 (fr) 1996-04-09 1997-04-09 Catalyseur de polymerisation d'olefines, procede de polymerisation d'olefines, compositions de polymeres d'olefines et articles thermoformes

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JP8/86699 1996-04-09
JP8/86698 1996-04-09
JP08669896A JP3749756B2 (ja) 1996-04-09 1996-04-09 オレフィン重合用触媒およびオレフィンの重合方法
JP8669996A JPH09278824A (ja) 1996-04-09 1996-04-09 オレフィン重合用触媒およびオレフィンの重合方法
JP08865896A JP3650463B2 (ja) 1996-04-10 1996-04-10 オレフィン重合体組成物
JP8/88659 1996-04-10
JP08865996A JP3650464B2 (ja) 1996-04-10 1996-04-10 オレフィン重合体組成物
JP8/88658 1996-04-10

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US6844446B2 (en) 2000-02-18 2005-01-18 Eastman Chemical Company Catalysts containing per-ortho aryl substituted aryl or heteroaryl substituted nitrogen donors
US6946532B2 (en) 2000-02-18 2005-09-20 Eastman Chemical Company Catalysts containing per-ortho aryl substituted aryl or heteroaryl substituted nitrogen donors
US7056996B2 (en) 2000-02-18 2006-06-06 E. I. Du Pont De Nemours And Company Productivity catalysts and microstructure control
US6579823B2 (en) 2000-02-18 2003-06-17 Eastman Chemical Company Catalysts containing per-ortho aryl substituted aryl or heteroaryl substituted nitrogen donors
US6706891B2 (en) 2000-11-06 2004-03-16 Eastman Chemical Company Process for the preparation of ligands for olefin polymerization catalysts

Also Published As

Publication number Publication date
EP0893455B1 (fr) 2004-10-06
CA2251057A1 (fr) 1997-10-16
DE69731081T2 (de) 2005-10-06
CN1219177A (zh) 1999-06-09
EP0893455A1 (fr) 1999-01-27
DE69731081D1 (de) 2004-11-11
CN1105730C (zh) 2003-04-16
CN1178962C (zh) 2004-12-08
EP0893455A4 (fr) 2000-06-14
KR20000005320A (ko) 2000-01-25
KR100311595B1 (ko) 2001-12-17
US6136743A (en) 2000-10-24
CN1439657A (zh) 2003-09-03

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